Process for producing chlorinated phenoxytoluene derivatives

ABSTRACT

Phenoxytoluene derivative is chlorinated in a very high yield and selectivity in the presence of nitrogen-, sulfur-, phosphorus- or oxygen-containing compound which is capable of forming a charge-transfer complex with chlorine, chlorine radical or organic halogen compound, together with radical initiator and organic halogen compound.

This invention relates to a process for producing chlorinated phenoxytoluene derivatives in high yields and selectivities by chlorinating a methyl group on a side chain of phenoxytoluene derivatives. The chlorinated phenoxytoluene derivatives of this invention include both phenoxybenzyl chlorides and phenoxybenzal chlorides. These chlorinated phenoxytoluene derivatives are easily converted by hydrolysis to phenoxybenzyl alcohol derivatives or phenoxybenzaldehyde derivatives. Especially, m-phenoxybenzyl alcohol or m-phenoxybenzaldehyde is an important intermediate of agricultural chemicals and insecticides. Various processes have heretofore been reported for producing phenoxybenzyl alcohols and phenoxybenzaldehydes.

For example, several patents have already been filed on processes for producing chlorinated phenoxytoluene derivatives by chlorinating methyl group in a side chain of phenoxytoluene derivatives, which processes are deemed to be preferable industrically.

1. Japanese Published Examined Patent Application (Kokoku) Nos. 10,228/1976 and 45,573/1976 (U.S. Pat. No. 4,014,940) discloses a method of chlorinating directly m-phenoxytoluene with use of phosphorus halogenide at a high temperature of more than 220° C. This method, however, has an disadvantage of accompanying a reaction operation at a high temperature and consumption of a lot of energy. Moreover, in this process, selectivities are low in both phenoxybenzyl chlorides and phenoxybenzal chlorides and especially low in phenoxybenzal chlorides.

2. Japanese Published Unexamined Patent Application (Kokai) No. 95,623/1977 (U.S. Pat. No. 4,085,147) discloses the preparation of a mixture of m-phenoxybenzyl chloride and m-phenoxybenzal chloride by chlorinating m-phenoxytoluene with chlorine in carbon tetrachloride in the presence of a radical initiator. This process gives the contemplated products in rather low selectivities. Especially, selectivity of phenoxybenzal chloride is very low with accompanying a production of a lot of nuclear-chlorinated products.

3. Japanese Kokai No. 40,732/1978 (U.S. Pat. No. 4,108,904) describes halogenation of m-phenoxytoluene by use of sulfuryl chloride, chlorine or bromine as a halogenating agent in carbon tetrachloride. The process is carried out with use of a free radical initiator or a strong incandescent light source. However, selectivities are rather low in both m-phenoxybenzyl chloride and m-phenoxybenzal chloride and especially very low in m-phenoxybenzal chloride.

4. Japanese Kokai No. 46,929/1978 (U.S. Pat. No. 4,146,737) discloses a method of chlorinating m-phenoxytoluene on the side chain in carbon tetrachloride with use of sulfuryl chloride as a halogenating agent in the presence of a radical initiator. In this method, the contemplated products are obtained in rather low selectivities and m-phenoxybenzal chloride in very low selectivity.

5. Japanese Kokai No. 103,433/1978 (DT-OS No. 27 07 232) shows a halogenation of m-phenoxytoluene on the side chain in carbon tetrachloride with chlorine or bromine as a halogenating agent by use of ultraviolet rays. In this process, selectivities are also low. When phenoxybenzal halide is obtained in a rather high selectivity, a highly chlorinated trichloride derivatives are produced in a large amount.

6. Japanese Kokai No. 92,928/1979 (U.K. patent application No. 2,010,837 describes a process for preparing m-phenoxybenzyl chloride, which comprises reacting m-phenoxytoluene with chlorine in the presence of a sulphur-containing catalyst without using a radical initiator and at a temperature which is, or is equivalent to, 200° to 280° C. at atmospheric pressure. However, selectivity of m-phenoxybenzyl chloride is rather low and that of m-phenoxybenzal chloride is extremely low.

It is generally known that, in the chlorination of aromatic compounds, electrophilic substitution reactions in the benzene ring proceed in competition with radical substitution reactions on the side chain. This occurs also in the chlorination of phenoxytoluene derivatives. For example, in U.S. Pat. No. 4,085,147, it is shown that a lot of nuclear-chlorinated products are formed together with side chain-chlorinated products.

Further, phenoxybenzal chloride derivatives are converted to phenoxyphenyl trichloromethane derivatives with a progress of chlorination. Accordingly, it is necessary to restrict the formation of the trichloride derivatives simultaneously with the restriction of the chlorination in benzene ring in order to obtain phenoxybenzal chloride derivatives in an high yield and high selectivity.

An object of this invention is to provide a method of chlorinating a phenoxytoluene derivative on the side chain in an extremely high yield and high selectivity.

An object of this invention is to provide a method of chlorination of a phenoxytoluene derivative with accompanying a very small formation of nuclear-chlorinated products and phenoxyphenyl trichloromethane derivatives.

Another object of this invention is to provide a method of chlorinating a phenoxytoluene derivative in which each of phenoxybenzyl chloride and phenoxybenzal chloride derivative is obtained in a very high yield and high selectivity.

These and other objects of the invention will become apparent from the following description.

The present invention provides a process for preparing a chlorinated phenoxytoluene derivative represented by the formula ##STR1## wherein R¹ and R² are the same or different and are each hydrogen, halogen, cyano, nitro, alkyl, alkoxyl, alkoxycarbonyl, halogenoalkyl, acyl, acyloxy, aryl, aralkyl or aralkyloxy, R³ is hydrogen or chlorine, characterized by chlorinating with chlorine a phenoxytoluene derivative represented by the formula ##STR2## wherein R¹ and R² are same as above, in the presence of at least one compound selected from the group consisting of nitrogen-containing compound, sulfur-containing compound, phosphorus-containing compound and oxygen-containing compound which is capable of forming a charge-transfer complex with chlorine, chlorine radical or organic halogen compound, together with radical initiator and organic halogen compound.

According to this invention, both of phenoxybenzyl chloride derivatives and phenoxybenzal chloride derivatives are prepared in an extremely high yield and high selectivity compared with the afore-mentioned conventional processes. Nuclear-chlorinated products and phenoxyphenyl trichloromethane derivatives, by-products, are restricted in an amount of usually less than 2 to 3%, respectively. These findings are quite novel which are not seen in conventional processes.

The chlorinated phenoxytoluene derivatives obtained by the present process are represented by the formula (1). In the groups R¹ to R², preferable examples of halogen are chlorine and bromine. Preferable examples of alkyl are those having 1 to 4 carbon atoms such as methyl, ethyl and butyl. Examples of preferable alkoxyl are those having 1 to 4 carbon atoms such as methoxy and propoxy. Examples of alkoxycarbonyl are those having 2 to 5 carbon atoms such as methoxycarbonyl and butoxycarbonyl. Halogenoalkyl has preferably 1 to 4 carbon atoms and includes for example chloromethyl and bromoethyl. Preferable examples of the group acyl both in acyl and acyloxy are those having 2 to 8 carbon atoms such as acetyl, propionyl, benzoyl and toluoyl. Examples of preferable aryl are those having 6 to 9 carbon atoms such as phenyl, tolyl and xylyl. Preferable examples of the group aralkyl both in aralkyl and aralkyloxy are those having 7 to 10 carbon atoms such as benzyl, phenylethyl and phenylpropyl.

Nitrogen-containing compounds useful in this invention are a wide variety of compounds represented by the following formulae. ##STR3## Preferable examples of R⁴ to R⁶ are hydrogen; alkyl having 1 to 20 carbon atoms such as methyl, butyl, octyl, dodecyl, hexadecyl, stearyl, etc; hydroxyalkyl having 1 to 10 carbon atoms such as hydroxymethyl, hydroxypropyl, hydroxyheptyl, etc; cycloalkyl having 5 to 8 carbon atoms such as cyclohexyl, cycloheptyl etc; aryl having 6 to 10 carbon atoms with or without a substituent such as phenyl, tolyl, ethylphenyl, chlorophenyl, trichlorophenyl, bromophenyl, etc. Two or three of R⁴ to R⁶ may form a ring.

Preferable examples of R⁷ are alkylene having 2 to 8 carbon atoms such as ethylene, propylene, hexamethylene, etc; arylene having 6 to 10 carbon atoms such as phenylene, tolylene, dimethylphenylene, chlorophenylene, etc.

Examples of preferable nitrogen-containing compounds are triethylamine, isobutylamine, 1-methylpentylamine, di-n-octylamine, n-dodecylamine, n-hexadecylamine, stearylamine, diethanolamine, cyclohexylamine, aniline, N,N-diethylaniline, 2,4,5-trichloroaniline, p-toluidine, hexamethylenediamine, p-phenylenediamine, succinimide, piperidine, pyridine, quinoline, 2-imidazoline, ethyleneimine, hexamethylenetetramine, 3,5-di-n-heptyl-1,2,4-triazole, 2,4-di-(4-pyridyl)-6-methyl-s-triazine, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,4-diazabicyclo(2,2,2)octane, etc.

Useful sulfur-containing compounds of the invention are represented by the following formulae. ##STR4## Preferable examples of R⁸ and R⁹ are alkyl having 1 to 20 carbon atoms; cycloalkyl having 5 to 8 carbon atoms; aryl having 6 to 10 carbon atoms; heterocyclic group having nitrogen, sulfur, oxygen atom, etc. Further R⁸ and R⁹ may conjointly form an alicyclic or heterocyclic ring, a is an integer of 1 to 8. A and B is R¹¹, NR¹² R¹³, NR¹² NR¹² R¹³, NR¹² NCR¹² R¹³, SR¹², SNR¹² R¹³, SHNR¹² R¹³ R¹⁴ or OR¹⁴, R¹⁰ to R¹⁴ are hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic ring and R¹² and R¹³ or R¹² to R¹⁴ may conjointly form a heterocyclic ring. R¹² and R¹³ further include acyl having 1 to 20 carbon atoms with or without a substituent and R¹¹ does not include hydrogen. A and B may conjointly form an alicyclic or heterocyclic ring. D is NR¹², sulfur atom or oxygen atom, E is R¹⁵, R¹⁵ SR¹⁵, R¹⁵ SO₂ R¹⁵, C(S)NHR¹⁵ NHC(S), R¹⁵ NHC(S)NHR¹⁵, R¹⁵ NR¹² R¹⁵, R¹⁵ C(O)R¹⁵ or R¹⁵ C(S)R¹⁵, b is 0 or an integer of 1 to 4 but b is 1 when D is NR¹² or oxygen atom, c is 0 or 1. F is R¹⁶, CN, NR¹⁷ R¹⁸, C(O)R¹⁷, S(O)R¹⁷, C(O)OR¹⁷, C(O)NR¹⁷ R¹⁸, C(O)SR¹⁷, R¹⁹ C(O)OR¹⁷, R¹⁹ C(O)NR¹⁷ R¹⁸ , R¹⁹ SR¹⁷ R¹⁹ NR¹⁷ R¹⁸, R¹⁹ C(O)R¹⁷ or HNR¹⁷ R¹⁷ R¹⁸, R¹⁶ to R¹⁸ are hydrogen; alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic group with or without a substituent; but R¹⁶ is alkyl, aryl or alicyclic group having a substituent when f is 0, R¹⁹ is alkylene having 1 to 12 carbon atoms or arylene having 6 to 10 carbon atoms with or without a substituent. G is R¹⁹, R¹⁹ C(O)R¹⁹, C(O)R¹⁹ C(O) or C(O), L is sulfur atom or NR¹⁷, d is 1 to 8, e is 1 to 50 and f is 0 or 1 to 50, and F further includes R¹⁹ OR¹⁷ and R¹⁹ OR¹⁹ OR¹⁹ when d is other than 1. In the above, as the groups alkyl, cycloalkyl, aryl, alkylene and arylene, the same are usable as those described in the nitrogen-containing compounds. As the acyl group in the definition of the above A and B, acetyl, butyryl, stearoyl, benzoyl, toluoyl and like acyl groups are enumerated.

Preferable examples of sulfur-containing compounds are isobutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, n-hexadecyl mercaptan, stearyl mercaptan, cyclohexyl mercaptan, thiophenol and like mercaptans; diisopropyl sulfide, di-n-octyl sulfide, di-n-dodecyl sulfide, di-n-hexadecyl sulfide, distearyl sulfide, diphenyl sulfide, dicyclohexyl sulfide, 2,2'-dipyridyl sulfide and like monosulfides; di-tert-butyl disulfide, di-n-octyl disulfide, di-n-dodecyl disulfide, di-n-hexadecyl disulfide, distearyl disulfide, diphenyl disulfide, dicyclohexyl disulfide, 2,2'-benzothiazolyl disulfide, diethyl tetrasulfide and like polysulfides; 2-mercaptobenzothiazole, tetrahydrothiophene, thiophene, 2-n-dodecyl-1,3,5-trithiane, 2-phenyl-1,3-dithian, 4-methylthiacyclohexane and like cyclic sulfur compounds; methyl cyclohexyl thioketone, 4,4'-bis(N,N-dimethylamino)thiobenzophenone, cyclohexanethion, 1-(n-heptadecyl)-2-thiourea, 1-isopropyl-3-(n-dodecyl)-2-thiourea, 1-(n-dodecanoyl)-2-thiourea, 1,3-dicyclohexyl-2-thiourea, 1-(p-tolyl)-3-(2-pyridyl)-2-thiourea, 1,1,3,3-tetra-n-propyl-2-thiourea, 1,4-diethyl-1,4-diphenyl-3-thiosemicarbazide, 1-isonicotinoyl-4-(n-octadecanoyl)-3-thiosemicarbazide, 1-(n-dodecanoyl)-4-(p-isoamyloxyphenyl)-3-thiosemicarbazide, 1-ethoxycarbonylmethyl-1-phenyl-4-ethyl-3-thiosemicarbazide, 1-(n-heptadecyl)-4-thiosemicarbazone, 1-(3-pyridyl)-5-ethyl-4-thiosemicarbazone, 1-pentamethylene-4-thiosemicarbazone, 1,5-diphenyl-3-thiocarbohydrazide, dithizone, 1,1,7,7-tetraphenyl-4-bisthiocarbohydrazone, 1,7-di-n-heptadecyl-4-bisthiocarbohydrazone, 1,7-dipentamethylene-4-bisthiocarbohydrazone, 5-ethyl-2-thiobiuret, 5-phenyl-1-(p-chlorophenyl)-2-thiobiuret, 5-(n-propyl)-2,4-dithiobiuret, N,N',N",N'"-hexamethylguanyl thiourea, 1-benzoyl-2-guanyl thiourea, thioacetanilide, thiobenzamide, thiobenzanilide, n-heptadecylthioamide, N-cyclohexylthiobenzamide, 2-benzothiazolylethyl thioanilide, thiophenylacetohydrazide, methylphenylthio-n-valerohydrazone, 2,4-dichlorophenylthiophenylacetohydrazone, N-(n-octyl)-N-aminoethyl dithiocarbamic acid, n-heptadecyl dithiocarbamic acid n-heptadecylammonium salt, 2-thiazolyldithiocarbamic acid triethylammonium salt, N-pentamethylene dithiocarbamic acid piperidinium salt, cyclohexyldithiocarbamic acid cyclohexylammonium salt, N,N-dimethyl S-(n-hexadecyl)dithiocarbamate, N,N-dimethyl S-(2-benzothiazolyl)dithiocarbamate, N-pentamethylene S-mercaptoethyl dithiocarbamate, N-diethyleneoxy S-hydroxyethyl dithiocarbamate, O-cyclohexylthioncarbamate, N-carboxymethyl O-(n-hexadecyl)thioncarbamate, N-pentamethylene O-(n-propyl)thioncarbamate, diethyl dithiocarbamyl sulfenamide, methylphenyl dithiocarbamyl sulfenamide, benzyl thionpropionate, methylthion cyclohexane carboxylate, isoamyl p-thiontoluate, dithiobenzoic acid, ethyl dithio-n-heptanoate, n-butyl dithiocyclohexanecarboxylate, carboxymethyldithio acid phenylacetate, n-dodecyl phenylthioncarbonate, tetramethylenethioncarbonate, diphenylthioncarbonate, di-n-octadecyl trithiocarbonate, di-n-dodecyl trithiocarbonate, di(4-chlorophenyl)trithiocarbonate, dicyclohexyl trithiocarbonate, S,O-(di-n-dodecyl)-xanthate, S-carboxydecamethylene O-(n-dodecyl)xanthate, S-(n-hexadecyl) O-cyclohexyl xanthate, S-lauroyl O-ethylxanthate, O-cyclohexylthion carbazate, 1-(n-dodecylidene) O-ethylthioncarbazate, 1-(n-dodecylidene) S-ethyldithiocarbazate, isobutyl isothiocyanate, n-octyl isothiocyanate, cyclohexyl isothiocyanate, p-(N,N-dimethylamino)phenyl isothiocyanate, 6-isothiocyanoquinoline, isothiocyanocapric acid methyl ester, ethylene diisothiocyanate, hexamethylene diisothiocyanate, methylenebis(N,N-dimethyldithiocarbamate), p-xylylenebis(N,N-dimethyldithiocarbamate), N,N-bis(N',N'-dimethylthiocarbamoylthioethyl)methylamine, bis(N,N-dimethylthiocarbamoylthioethyl)sulfide, p,p'-bis(dithiocarbamoyl)diphenyl sulfone, 1,4-phenylenebisisopropyl thiourea, dimethylene trithiourea, methylenebistetramethylene thiourea, bis(N-trimethylenethioacetamide), ethylenebisdithiocarbamic acid diammonium salt, diisopropyldithion oxalate, S,S'-diethyl O,O'-decamethylenebisxanthate, O,O'-dicyclohexyl S,S'-methylenebisxanthate, O,O'-di(n-octyl) S,S'-(p-xylylene)bisxanthate, cyclohexylxanthogene monosulfide, ethoxyethylxanthogene monosulfide, n-hexadecyl dixanthogene, benzyl dixanthogene, ethyl dixanthogene disulfide, O-ethylthiooxalamide, N,N'-dimorpholinodithiooxalic diamide, N,N-di(n-dodecyl)dithiooxalic diamide, N,N'-diphenyldithio(n-butyl)malonic diamide, N,N'-di-n-octyldithioadipic diamide, bis(piperidinothiocarbonyl)monosulfide, bis(morpholinothiocarbonyl)monosulfide, bis(hydrazinothiocarbonyl)monosulfide, bis(n-octylidenehydrazinothiocarbonyl)monosulfide, bis(di-n-butylthiocarbamoyl)disulfide, bis(piperidinothiocarbonyl)disulfide, bis(morpholinothiocarbonyl)disulfide, ethylene-1,2-bis[1,2-(dithiocarbamoyl)ethylene]disulfide, ethylene-1,2-bis(benzothiazolylthiocarbamoyl)disulfide, bis(dimethylthiocarbamoyl)tetrasulfide, bis(piperidinothiocarbonyl)hexasulfide, n-octadecyl thiocyanate, pentamethylene dithiocyanate, 2-chlorocyclohexyl thiocyanate, p-aminophenyl thiocyanate, 3-thiocyanopyridine, N-diethyleneoxy-2-benzothiazolyl sulfenamide, N-(n-heptadecyl)-n-octyl sulfenamide, N-tert-butyl-2-benzothiazolyl sulfenamide, N-cyclohexyl-2-benzothiazolyl sulfenamide, di-n-amyl thiosulfinate, tert-butylethyl thiosulfinate, thiostearic acid, thioterephthalic acid, cyclohexylthiol acetate, N,N-diethylaminoethylthiolphenylacetate, dicyclohexyldithiosebacate, 1,6-hexamethylenedithiol diacetate, S-phenacyl O-ethylthiolcarbonate, S,S'-dimethylenecarboxy O,O'-diethylbisthiolcarbonate, diphenyl dithiolcarbonate, N-(ζ-aminohexamethyl)thiocarbamic acid, N-phenylthiocarbamic acid, N-stearylthiocarbamic acid stearylammonium salt, N-isobutylthiocarbamic acid isobutylammonium salt, N-pentamethylene S-phenylthiol carbamate, N-cyclohexyl S-pentamethylenethiol carbamate, S,S'-pentamethylenebisthiol carbamate, n-hexylmercaptocapric acid, 2-thienylmercaptoacetic acid, n-octadecylmercaptosuccinic acid diethyl ester, 2-thienylmercaptoacetic acid n-dodecyl ester, methylmercaptopelargonic acid amide, n-octylmercaptobenzamide, S,S'-di(n-octadecyl)methyl thioacetal, S,S'-dibenzylcyclohexyl ketone thioacetal, ethylenebis(S,S'-di-n-octadecylmethyl)ketone thioacetal, tri-n-dodecyl trithioorthoformate, triphenyltrithioorthobenzoate, tetraisopropyl tetrathioorthocarbonate, tetracyclohexyl tetrathioorthocarbonate, di(β-chloroethyl)sulfide, 1,10-decamethylenebischloroethyl sulfide, γ-chloro-γ'-(N,N-diethylamino)dipropyl sulfide, N-(n-octadecyl)iminomethylethyl sulfide, di(N-pentamethyleneaminoethyl)sulfide, n-butylmercaptoacetaldehyde, p-benzylmercaptobenzaldehyde, n-dodecylmercaptomethyl phenyl ketone, bis(n-heptylcarbonylmethyl)sulfide, n-octadecylmercaptopropionitrile, di(chloroacetyl)sulfide, dibenzoyl sulfide, ethylenebis(β-cyanoethyl sulfide), 1,18-octadecamethylene bis(n-octadecyl sulfide), bis{2-[2-(2-chloroethylthio)ethylthio]ethyl}sulfide, poly(ethylenesulfide), poly(phenylenesulfide), α,α'-di-n-hexadecyldi(carboxymethyl)disulfide, di(κ-carboxydecyl)disulfide, di(cyclohexyloxycarbonylethyl)disulfide, di(n-octadecyloxycarbonylethyl)disulfide, di(N-methyolanilinocarbonylmethyl)disulfide, di(γ-carbamoylpropyl)disulfide, di(ζ-chlorohexyl)disulfide, di(2,4-dichlorophenyl)disulfide, di(N,N-dimethylaminohexamethyl)disulfide, di(m-aminophenyl)disulfide, di(α-formylisopropyl)disulfide, di(o-formylmethylthiophenyl)disulfide, di(methylcarbonylisobutyl)disulfide, di(2-methylcarbonyl-5-methoxyphenyl)disulfide, di(p-cyanophenyl)disulfide, ζ-cyano-ζ'-hydroxy dihexamethyl disulfide, dibenzoyl disulfide, di-3-nicotinoyl disulfide, poly(ethylformal disulfide), poly(ethylene disulfide), di(γ-hydroxypropyl)disulfide, di(m-hydroxyphenyl)disulfide, di(β-ethoxyethyl)disulfide, di(2-ethoxy-1-naphthyl)disulfide, di(carboxymethyl)trisulfide, di(o-carboxyphenyl)tetrasulfide, di(p-ethoxycarbonylphenyl)trisulfide, di(n-dodecyloxycarbonylmethyl)tetrasulfide, di(carbamoylmethyl)trisulfide, di(o-n-butylcarbamoylphenyl)tetrasulfide, di(β-chloroethyl)tetrasulfide, di(β-chloroethyl)pentasulfide, di(p-aminophenyl)trisulfide, di(ethylenediaminoethyl)tetrasulfide, di(β-formylethyl)trisulfide, di(m-formylphenyl)trisulfide, di(acetylmethyl)trisulfide, di(3-acetyl-4-hydroxy-1-naphthyl)trisulfide, di(β-cyanoethyl)trisulfide, di(p-cyanophenyl)trisulfide, dibenzoyl tetrasulfide, diacetyl tetrasulfide, poly(ethylene pentasulfide), poly(oxydiethylene tetrasulfide), di(β-hydroxyethyl)trisulfide, di(2-hydroxy-1-naphthyl)trisulfide, di(n-dodecyloxyethyl)trisulfide, di(2-ethoxy-1-naphthyl)trisulfide, α-mercaptostearic acid, κ-mercaptoundecylic acid, n-octadecyl mercaptoacetate, ethyl mercaptosuccinate, methyl p-mercaptobenzoate, α-mercaptopropionanilide, ε-mercaptocaproic acid amide, 2,3-dichloropropyl mercaptan, pentachlorothiophenol, β-mercaptoethyl n-dodecylamine, N,N-di(γ-mercaptoisobutyl)piperazine, β-formylethyl mercaptan, α-phenyl-β-formylethyl mercaptan, di(p-mercaptophenyl)ketone, mercaptomethyl n-hexyl ketone, β-cyanoethyl mercaptan, p-cyanothiophenol, bis(ethylenedimercaptomethyl)methane, 2-n-heptylmercaptocyclohexanethiol, di(β-mercaptoethyl)disulfide, p-hydroxy-p'-mercaptodiphenyl disulfide, di(2-mercapto-1-naphthyl)trisulfide, di(β-mercaptoethyl)tetrasulfide, 1,6-hexamethylene dithiol, 1,18-octadecamethylene dithiol, 1,2-cyclohexane dithiol, 3,4-thiophene dithiol, etc.

Phosphorus-containing compounds employed in the invention are represented by the following formulae. ##STR5## Preferable examples of M, Q and T are hydrogen, halogen, R²⁰, WR²⁰ or NR²⁰ R²¹, R²⁰ and R²¹ are the same or different and are hydrogen, alkyl having 1 to 20 carbon atoms; aryl having 6 to 10 carbon atoms; amino; alicyclic or heterocyclic ring, W is oxygen atom or sulfur atom, and M and Q, or Q and T may conjointly form an alicyclic or heterocyclic ring, and at least two of M, Q and T are organic group other than hydrogen. In the above, examples of halogen are chlorine, bromine, etc. As the groups alkyl and aryl, the same are usable as those described in the nitrogen-containing compounds.

Examples of preferable phosphorus-containing compounds are tri-n-butylphosphine, tri-n-octylphosphine, tri-n-dodecylphosphine, n-octadecyldiphenylphosphine, triphenylphosphine, 1-mercaptoethyldiphenylphosphine, tricyclohexylphosphine, dicyclohexyl 4-chlorophenylphosphine, triisopropylphosphine sulfide, n-hexadecyldiphenylphosphine sulfide, triphenylphosphine oxide, tri-n-dodecylphosphine oxide, N,N-diethylhydrazinodiphenylphosphine oxide, 1-phenyl-1-phosphacyclohexane, n-octadecyl diphenyl phosphite, dicyclohexyl chloro phosphite, di-n-octyl phosphite, diphenyl cyclohexyl phosphite, triphenyl phosphite, tricyclohexyl phosphite, diiosopropyl chloro thiophosphite, tricyclohexyl thiophosphite, tri-n-dodecyl thiophosphite, triphenyl thiophosphite, tris(dimethylamino)phosphine, phosphorus tripiperidide, tris(di-n-butylamino)phosphine, phosphorus tri(N-methylanilide), diphenylphosphinic chloride, cyclohexylphenylphosphinothioic chloride, di-n-butylphosphinothioic acid, isopropyl n-hexyl phosphinic acid, dicyclohexylphosphinodithioic acid, methyl n-octyl n-hexyl phosphinate, O-methyl diisopropylphosphinothioate, phenyl diethylphosphinodithioate, methyl dicyclohexyl phosphinate, hexamethylene phosphoric triamide, phenyl phosphonus dichloride, cyclohexylphosphonic dichloride, S,S-diethyl phenylphosphonodithioate, diethyl-n-butylphosphonate, O,O-diethyl phenylphosphonothioate, O,S-diethyl phenylphosphonothioate, S-ethyl N,N-diethyl P-methyl phosphonamide thioate, O-ethyl phenyl phosphonodithioate, O-ethyl S-phenyl phenylphosphonodithioate, etc.

Useful oxygen-containing compounds of this invention are represented by the following formulae. ##STR6## Preferable examples of R²² and R²³ are alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic of heterocyclic ring, and R²² and R²³ may form an alicyclic, heterocyclic or large polyether ring. R²⁴ and R²⁵ are the same or different and are alkylene having 2 to 8 carbon atoms, X is hydrogen atom, sulfur atom, alkoxyl, alkylamino or alkylamido, each having 1 to 20 carbon atoms and with or without a substituent, aryloxy having 6 to 10 carbon atoms, oxyalicyclic or oxyheterocyclic ring, each having or not having a substituent, Y is hydrogen, halogen, hydroxyl, mercapto, alkyl having 1 to 20 carbon atoms, carboxylalkyl having 2 to 20 carbon atoms or alkylamino having 1 to 20 carbon atoms, Z is oxygen atom or sulfur atom, g is 1 to 50, h is 0 to 25 and i is 1 to 6 but i is 2 when X is oxygen atom or sulfur atom. In the above, as halogen, alkyl, aryl, alkyl in the groups alkoxyl, alkylamino, alkylamido and carboxyalkyl, aryl in the group aryloxy, the same are usable as those in the aforementioned nitrogen- or sulfur-containing compounds. Examples of oxyalicyclic and oxyheterocyclic ring are cyclohexyloxy, pyridyloxy, quinolyloxy, etc. In the invention are excluded ethers having boiling point of less than 70° C.

Preferable examples of oxygen-containing compounds are 2,2'-dichlorodiethyl ether, di-n-butyl ether, di-n-octyl ether, di-n-octadecyl ether, diphenyl ether, naphthyl ethyl ether, dicyclohexyl ether, 4-pyridyl ethyl ether, p-dioxane, furan, tetrahydrofuran, 15-crown-5, dibenzo-18-crown-6, isobutyl alcohol, n-octyl alcohol, n-tetradecyl alcohol, n-octadecyl alcohol, m-cresol, 2,6-di-tert-butyl-4-methyl phenol, 2-(3-tolyoxy)-3-methyl phenol, 2,2'-methylenebis(4-methoxy-6-tert-butyl phenyl), 4,4'-thiobis(3-methyl-6-tert-butyl phenol), 4-hydroxypyridine, cyclohexyl alcohol, ethylene glycol, ethylene dithioglycol, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-dodecyl ether, propylene glycol diisopropionate, tripropylene glycol monostearate, ethylene glycol monophenyl ether, β-cyclodextrin, 1,5-sorbitan monostearate, glycerin monopalmitate, bis(hydroxyethylthioethyl)ether, bis(mercaptoethylthioethyl)ether, bis(chloroethoxyethyl)ether, bis(aminoethylthioethyl)ether, ethylene dithioglycol hexamer, polyethylene glycol, polypropylene glycol, polyoxyethylene 1,5-sorbitan monostearate, polyoxyethylene glycerin monoplamitate, polyoxyethylene dodecyl ether, polyoxyethylene p-dodecylphenyl ether, polyoxyethylene laurylamine, polyoxyethylene laurylamide, etc.

In this invention, the above-mentioned nitrogen-, sulfur-, phosphorus- and oxygen-containing compounds are capable of forming charge-transfer complex with chlorine, chlorine radical or organic halogen compounds. These N, S, P and O-containing compounds are usable singly or at least two of them are usable, and are used in an amount of about 0.001 to 50 wt %, preferably about 0.01 to 30 wt % based on the starting phenoxytoluene derivative. With use of the above-mentioned range of the compound, the contemplated reaction proceeds effectively.

Examples of useful organic halogen compounds are represented by the formulae below. ##STR7## In the above, Hal means halogen atom such as chlorine, bromine, iodine, etc., m is 0 or an integer of 1 to 3, m' is 0 or an integer of 1 to 2, m" is 0 or 1, n is an integer of 1 to 6.

Preferable examples of organic halogen compounds are carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, chloroform, bromoform, iodoform, methylene chloride, methylene bromide, dichloroethane, trichloroethane, tetrachloroethane, tetrachloroethylene, hexachlorocyclohexane, etc. Chlorinated paraffin is also included in organic halogen compound of the invention. More preferable organic halogen compound are carbon tetrachloride and carbon tetrabromide. These organic halogen compounds are usable singly or at least two of them are usable, and are used in an amount of usually 1 to 20 times, preferably 5 to 10 times the weight of the starting phenoxytoluene derivative.

Useful radical initiators of the invention are azo compounds or peroxides, and preferably are azobisisobutyronitrile, benzoyl peroxide, etc. The radical initiator is used in an amount of usually about 0.001 to 20 wt %, preferably about 0.01 to 15 wt % of the phenoxytoluene derivative. It is preferable to blow chlorine into the reaction system in an amount of about 0.5 to 10 mole %, preferably about 2 to 5 mole % of the phenoxytoluene derivative in a minute until the reaction is completed. The reaction is conducted at usually about 0° to 150° C., preferably at a temperature of reflux state of the reaction mixture.

The desired compound of the invention is easily purified by known methods such as concentration, extraction, distillation, recrystallization, column chromatography, etc.

The invention will be described below in greater detail with reference to the following examples.

EXAMPLE 1

Into a flask equipped with a thermometer, stirrer, gas-introducing pipe and reflux condenser are placed 95 g (0.52 mole) of m-phenoxytoluene, 10 g of azobisisobutyronitrile, 1 g of piperidine and 1,300 g of carbon tetrachloride. The mixture is heated with stirring at a temperature of 78° to 82° C. to bring the system in a mildly reflux state. To the flask are blown 0.023 mole/min. of chlorine and the mixture is reacted for one hour. After completion of the reaction, the mixture is cooled. The carbon tetrachloride is distilled off at a reduced pressure, giving a slightly yellow product. Analysis of the product by gas chromatography shows 1.2% (yield, same in hereinafter) of m-phenoxybenzyl chloride, 95.0% of m-phenoxybenzal chloride, 2.8% of m-phenoxyphenyl trichloromethane and 1.0% of nuclear-chlorinated compounds. For comparison, the same reaction is carried out with exception that piperidine is not added. The result shows 70.8% of m-phenoxytoluene, 28.2% of m-phenoxybenzyl chloride, 0% of m-phenoxybenzal chloride and 1.0% of nuclear-chlorinated compounds.

EXAMPLES 2 TO 17

Reactions are conducted in a similar manner as in Example 1 with use of typical phenoxytoluene derivatives in Table 1. The results are also shown in Table.

                  TABLE 1                                                          ______________________________________                                         Chlorination of phenoxytoluenes in the coexistence                             of piperidine                                                                                     Reac.                                                       EX.  Starting material                                                                            time                (yield,                                 No.  (g)           (min.)  Products    %)                                      ______________________________________                                         2    m-phenoxytoluene                                                                             30      m-phenoxytoluene                                                                           (3.4)                                        (95)                  m-phenoxybenzyl                                                                chloride    (92.6)                                                             m-phenoxybenzal                                                                chloride    (3.3)                                                              nucleus-substituted                                                                        (0.7)                                   3    p-phenoxytoluene                                                                             60      p-phenoxybenzyl                                          (95)                  chloride    (1.7)                                                              p-phenoxybenzal                                                                chloride    (94.0)                                                             p-phenoxyphenyl                                                                trichloromethane                                                                           (2.2)                                                              nucleus-substituted                                                                        (2.1)                                   4    3-phenoxy-6-chloro-                                                                          72      3-phenoxy-6-chloro-                                      toluene               benzyl chloride                                                                            (7.5)                                        (114)                 3-phenoxy-6-chloro-                                                            benzal chloride                                                                            (90.5)                                                             3-phenoxy-6-chloro-                                                            phenyl trichloro-                                                              methane     (1.0)                                                              nucleus-substituted                                                                        (1.0)                                   5    m,m'-dimethyldi-                                                                             120     m,m'-di(chloro-                                          phenyl ether          methyl)diphenyl                                          (103)                 ether       (2.2)                                                              m,m'-di(dichloro-                                                              methyl)diphenyl                                                                ether       (90.6)                                                             m,m'-di(trichloro-                                                             methyl)diphenyl                                                                ether       (4.7)                                                              nucleus-substituted                                                                        (2.5)                                   6    m-(m-chloromethyl-                                                                           72      m-(m-chloromethyl-                                       phenoxy)toluene       phenoxy)toluene                                                                            (5.3)                                        (121)                 m-(m-dichloro-                                                                 methylphenoxy)                                                                 benzyl chloride                                                                            (90.3)                                                             m-(m-trichloro-                                                                methylphenoxy)                                                                 benzal chloride                                                                            (3.4)                                                              nucleus-substituted                                                                        (1.0)                                   7    m-(p-benzoylphen-                                                                            36      m-(p-benzoylphen-                                        oxy)toluene           oxy)toluene (4.3)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzyl chloride                                                                        (91.5)                                                             m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (3.2)                                                              nucleus-substituted                                                                        (1.0)                                   8    m-(p-benzoylphen-                                                                            72      m-(p-benzoylphen-                                        oxy)toluene           oxy)benzyl chloride                                                                        (3.5)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (93.0)                                                             m-(p-benzoylphen-                                                              oxy)phenyl tri-                                                                chloromethane                                                                              (2.3)                                                              nucleus-substituted                                                                        (1.2)                                   9    m-(p-cyanophenoxy)                                                                           72      m-(p-cyanophenoxy)-                                      toluene               benzyl chloride                                                                            (1.9)                                        (109)                 m-(p-cyanophenoxy)-                                                            benzal chloride                                                                            (91.6)                                                             m-(p-cyanophenoxy)-                                                            phenyl trichloro-                                                              methane     (4.8)                                                              nucleus-substituted                                                                        (1.7)                                   10   m-(p-nitrophenoxy)                                                                           84      m-(p-nitrophenoxy)-                                      toluene               benzyl chloride                                                                            (6.8)                                        (119)                 m-(p-nitrophenoxy)-                                                            benzal chloride                                                                            (89.2)                                                             m-(p-nitrophenoxy)-                                                            phenyl trichloro-                                                              methane     (3.3)                                                              nucleus-substituted                                                                        (0.7)                                   11   m-(p-phenylphen-                                                                             36      m-(p-phenylphen-                                         oxy)toluene           oxy)toluene (4.2)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzyl chloride                                                                        (92.7)                                                             m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (2.8)                                                              nucleus-substituted                                                                        (0.3)                                   12   m-(p-phenylphen-                                                                             72      m-(p-phenylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (3.1)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (92.1)                                                             m-(p-phenylphen-                                                               oxy)phenyl                                                                     trichloromethane                                                                           (3.3)                                                              nucleus-substituted                                                                        (1.5)                                   13   m-(p-benzylphen-                                                                             72      m-(p-benzylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (1.2)                                        (143)                 m-(p-benzylphen-                                                               oxy)benzal chloride                                                                        (93.7)                                                             m-(p-benzylphen-                                                               oxy)phenyl                                                                     trichloromethane                                                                           (3.1)                                                              nucleus-substituted                                                                        (2.0)                                   14   m-(p-benzyloxy-                                                                              72      m-(p-benzyloxy-                                          phenoxy)toluene       phenoxy)benzyl                                           (151)                 chloride    (2.7)                                                              m-(p-benzyloxy-                                                                phenoxy)benzal                                                                 chloride    (91.6)                                                             m-(p-benzyloxy-                                                                phenoxy)phenyl                                                                 trichloromethane                                                                           (4.0)                                                              nucleus-substituted                                                                        (1.7)                                   15   p-(m-tolyloxy)                                                                               72      p-(m-chloromethyl-                                       phenyl benzoate       phenoxy)phenyl                                           (158)                 benzoate    (2.1)                                                              p-(m-dichloro-                                                                 methylphenoxy)-                                                                phenyl benzoate                                                                            (92.7)                                                             p-(m-trichloro-                                                                methylphenoxy)-                                                                phenyl benzoate                                                                            (3.6)                                                              nucleus-substituted                                                                        (1.6)                                   16   m-(p-methoxyphen-                                                                            35      m-(p-methoxyphen-                                        oxy)toluene           oxy)toluene (3.2)                                        (111)                 m-(p-methoxyphen-                                                              oxy)benzyl chloride                                                                        (92.7)                                                             m-(p-methoxyphen-                                                              oxy)benzal chloride                                                                        (3.1)                                                              nucleus-substituted                                                                        (1.0)                                   17   m-(p-methoxycar-                                                                             35      m-(p-methoxy-                                            bonyl phenoxy)-       carbonyl phenoxy)-                                       toluene               toluene     (5.4)                                        (126)                 m-(p-methoxy-                                                                  carbonyl phenoxy)-                                                             benzyl chloride                                                                            (90.3)                                                             m-(p-methoxy-                                                                  carbonyl phenoxy)-                                                             benzal chloride                                                                            (2.7)                                                              nucleus-substituted                                                                        (1.6)                                   ______________________________________                                    

EXAMPLE 18

Chlorination reactions are conducted in a similar manner as in Example 1 with use of m-phenoxytoluene and typical nitrogen- of sulfur-containing compounds listed in Table 2. The results are also given in Table.

                  TABLE 2                                                          ______________________________________                                         Effect of nitrogen-containing and sulfur-containing                            compounds on the chlorination of m-phenoxytoluene                              Nitrogen-containing                                                                             Reac.                                                         or sulfur-containing                                                                            time    Products (Yield, %)                                   No.  compound        (hr)    (1) (2)  (3)  (4) (5)                             ______________________________________                                         1    Stearylamine    1       --  1.4  92.6 2.9 3.1                             2    Diethanolamine  1       --  1.6  93.7 2.6 2.1                             3    Cyclohexylamine 1       --  4.1  92.8 1.2 1.9                             4    N,Ndiethylaniline                                                                              0.5     3.3 92.6 3.2  --  0.9                             5    N,Ndiethylaniline                                                                              1       --  1.0  95.3 1.9 1.8                             6    Quinoline       1       --  2.8  93.4 2.1 1.7                             7    1,8-diazabicyclo(5,4,0)-                                                                       1       --  1.6  95.7 2.0 0.7                                  7-undecene                                                                8    1,4-diazabicyclo(2,2,2)                                                                        1       --  1.8  95.6 1.7 0.9                                  octane                                                                    9    Morpholine      0.5     5.4 90.4 3.1  --  1.1                             10   Morpholine      1       --  2.9  92.2 3.5 1.4                             11   Di-n-dodecyl sulfide                                                                           0.5     4.8 93.1 1.3  --  0.8                             12   Di-n-dodecyl sulfide                                                                           1       --  1.2  96.8 0.8 1.2                             13   Diphenyl sulfide                                                                               1       --  2.3  93.5 1.9 2.3                             14   Dicyclohexyl sulfide                                                                           1       --  1.9  93.9 3.2 1.0                             15   2,2'-dipyridyl sulfide                                                                         1       --  1.2  93.1 2.1 3.6                             16   Di-tert-butyl disulfide                                                                        1       --  9.1  87.9 2.2 0.8                             17   Diphenyl disulfide                                                                             1       --  5.1  90.6 2.4 1.9                             18   Dicyclohexyl disulfide                                                                         0.5     4.0 90.1 5.4  --  0.5                             19   Dicyclohexyl disulfide                                                                         1       --  3.1  94.7 1.3 0.9                             20   2,2'-dibenzothiazolyl                                                                          1       --  2.6  95.1 1.5 0.8                                  disulfide                                                                 21   Diethyl tetrasulfide                                                                           1       --  2.8  94.8 1.4 1.0                             22   Tetrahydrothiophene                                                                            1       --  4.7  91.2 2.1 2.0                             23   Thiophene       0.5     4.5 90.8 3.4  --  1.3                             24   Thiophene       1       --  3.6  92.7 1.9 1.8                             25   2-phenyl-1,3-dithian                                                                           1       --  2.7  93.4 2.7 1.2                             26   n-octyl mercaptan                                                                              1.2     --  4.0  92.8 2.3 0.9                             27   Cyclohexyl mercaptan                                                                           0.6     5.1 90.2 3.6  --  1.1                             28   Cyclohexyl mercaptan                                                                           1       --  2.9  91.8 3.6 1.7                             29   Thiophenol      1       --  4.8  90.3 2.9 2.0                             30   2-mercaptobenzothiazole                                                                        1       --  8.0  88.5 2.0 1.5                             ______________________________________                                          ##STR8##                                                                                                                                                      ##STR9##                                                                                                                                                      ##STR10##                                                                                                                                                     ##STR11##                                                                                                                                                     ##STR12##                                                                

EXAMPLE 19

The procedure of Example 1 is followed with use of 95 g (0.52 mole) of m-phenoxytoluene, 10 g of azobisisobutyronitrile, 1 g of N-pentamethylenedithiocarbamic acid piperidinium salt and 1,300 g of carbon tetrachloride. The reaction time is 75 minutes. Analysis of the product by gas chromatography shows 0.9% of m-phenoxybenzyl chloride, 96.8% of m-phenoxybenzal chloride, 1.3% of m-phenoxyphenyl trichloromethane and 1.0% of nuclear-chlorinated compounds. For comparison, the same reaction is conducted, except that the above piperidium salt is not used. The result shows 41.0% of m-phenoxytoluene, 45.7% of m-phenoxybenzyl chloride, 12.1% of m-phenoxybenzal chloride and 1.2% of nuclear-chlorinated compounds.

EXAMPLE 20

Exactly the same procedure as in Example 19 is followed except that 1 g of N-diethyleneoxy-2-benzothiazolyl sulfenamide is used in place of 1 g of N-pentamethylenedithiocarbamic acid piperidinium salt. The result shows 2.1% of m-phenoxybenzyl chloride, 95.6% of m-phenoxybenzal chloride, 1.8% of m-phenoxyphenyl trichloromethane and 0.5% of nuclear-chlorinated products. The similar reaction without the above sulfenamide gives 41.0% of m-phenoxytoluene, 45.7% of m-phenoxybenzyl chloride, 12.1% of m-phenoxybenzal chloride and 1.2% of nuclear-chlorinated compounds.

EXAMPLES 21 TO 36

Table 3 shows the results of reactions which are conducted in a similar manner as in Example 19 with use of typical phenoxytoluene derivatives.

                  TABLE 3                                                          ______________________________________                                         Chlorination of phenoxytoluenes in the coexistence of                          piperidinium salt of N--pentamethylenedithiocarbamic                           acid                                                                                              Reac.                                                            Starting material                                                                            time                (yield,                                 No.  (g)           (min.)  Products    %)                                      ______________________________________                                         21   m-phenoxytoluene                                                                             35      m-phenoxytoluene                                                                            (2.8)                                       (95)                  m-phenoxybenzyl                                                                chloride    (93.4)                                                             m-phenoxybenzal                                                                chloride    (2.9)                                                              nucleus-substituted                                                                        (0.9)                                   22   p-phenoxytoluene                                                                             75      p-phenoxybenzyl                                          (95)                  chloride    (2.0)                                                              p-phenoxybenzal                                                                chloride    (94.5)                                                             p-phenoxyphenyl                                                                trichloromethane                                                                           (2.0)                                                              nucleus-substituted                                                                        (1.5)                                   23   3-phenoxy-6-chloro-                                                                          85      3-phenoxy-6-chloro-                                      toluene               benzyl chloride                                                                            (5.6)                                        (114)                 3-phenoxy-6-chloro-                                                            benzal chloride                                                                            (91.3)                                                             3-phenoxy-6-chloro-                                                            phenyl trichloro-                                                              methane     (2.1)                                                              nucleus-substituted                                                                        (1.0)                                   24   m,m'-dimethyldi-                                                                             150     m,m'-di(chloro-                                          phenyl ether          methyl)diphenyl                                          (103)                 ether       (2.5)                                                              m,m'-di(dichloro-                                                              methyl)diphenyl                                                                ether       (89.8)                                                             m,m'-di(trichloro-                                                             methyl)diphenyl                                                                ether       (4.8)                                                              nucleus-substituted                                                                        (2.9)                                   25   m-(m-chloromethyl-                                                                           85      m-(m-chloromethyl-                                       phenoxy)toluene       phenoxy)toluene                                                                            (3.2)                                        (121)                 m-(m-dichloro-                                                                 methylphenoxy)                                                                 benzyl chloride                                                                            (91.0)                                                             m-(m-trichloro-                                                                methylphenoxy)                                                                 benzal chloride                                                                            (3.7)                                                              nucleus-substituted                                                                        (2.1)                                   26   m-(p-benzoylphen-                                                                            40      m-(p-benzoylphen-                                        oxy)toluene           oxy)toluene (3.9)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzyl chloride                                                                        (90.8)                                                             m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (4.2)                                                              nucleus-substituted                                                                        (1.1)                                   27   m-(p-benzoylphen-                                                                            80      m-(p-benzoylphen-                                        oxy)toluene           oxy)benzyl chloride                                                                        (2.8)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (93.7)                                                             m-(p-benzoylphen-                                                              oxy)phenyl tri-                                                                chloromethane                                                                              (2.0)                                                              nucleus-substituted                                                                        (1.5)                                   28   m-(p-cyanophenoxy)                                                                           85      m-(p-cyanophenoxy)-                                      toluene               benzyl chloride                                                                            (1.2)                                        (109)                 m-(p-cyanophenoxy)-                                                            benzal chloride                                                                            (92.1)                                                             m-(p-cyanophenoxy)-                                                            phenyl trichloro-                                                              methane     (4.3)                                                              nucleus-substituted                                                                        (2.4)                                   29   m-(p-nitrophenoxy)                                                                           85      m-(p-nitrophenoxy)-                                      toluene               benzyl chloride                                                                            (5.9)                                        (119)                 m-(p-nitrophenoxy)-                                                            benzal chloride                                                                            (90.2)                                                             m-(p-nitrophenoxy)-                                                            phenyl trichloro-                                                              methane     (2.4)                                                              nucleus-substituted                                                                        (1.5)                                   30   m-(p-phenylphen-                                                                             40      m-(p-phenylphen-                                         oxy)toluene           oxy)toluene (3.7)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzyl chloride                                                                        (91.0)                                                             m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (4.1)                                                              nucleus-substituted                                                                        (1.2)                                   31   m-(p-phenylphen-                                                                             80      m-(p-phenylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (3.9)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (92.5)                                                             m-(p-phenylphen-                                                               oxy)phenyl trichloro-                                                          methane     (2.0)                                                              nucleus-substituted                                                                        (1.6)                                   32   m-(p-benzylphen-                                                                             80      m-(p-benzylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (2.5)                                        (143)                 m-(p-benzylphen-                                                               oxy)benzal chloride                                                                        (93.6)                                                             m-(p-benzylphen-                                                               oxy)phenyl trichloro-                                                          methane     (1.8)                                                              nucleus-substituted                                                                        (2.1)                                   33   m-(p-benzyloxy-                                                                              80      m-(p-benzyloxy-                                          phenoxy)toluene       phenoxy)benzyl                                           (151)                 chloride    (2.2)                                                              m-(p-benzyloxy-                                                                phenoxy)benzal                                                                 chloride    (93.3)                                                             m-(p-benzyloxy-                                                                phenoxy)phenyl                                                                 trichloromethane                                                                           (2.7)                                                              nucleus-substituted                                                                        (1.8)                                   34   p-(m-tolyloxy)                                                                               80      p-(m-chloromethyl-                                       phenyl benzoate       phenoxy)phenyl                                           (158)                 benzoate    (1.8)                                                              p-(m-dichloro-                                                                 methylphenoxy)-                                                                phenyl benzoate                                                                            (94.5)                                                             p-(m-trichloro-                                                                methylphenoxy)-                                                                phenyl benzoate                                                                            (2.6)                                                              nucleus-substituted                                                                        (1.1)                                   35   m-(p-methoxyphen-                                                                            35      m-(p-methoxyphen-                                        oxy)toluene           oxy)toluene (3.9)                                        (111)                 m-(p-methoxyphen-                                                              oxy)benzyl chloride                                                                        (90.5)                                                             m-(p-methoxyphen-                                                              oxy)benzal chloride                                                                        (3.5)                                                              nucleus-substituted                                                                        (2.1)                                   36   m-(p-methoxycar-                                                                             35      m-(p-methoxycarbon-                                      bonyl phenoxy)-       yl phenoxy)toluene                                                                         (3.6)                                        toluene               m-(p-methoxycarbon-                                      (126)                 yl phenoxy)benzyl                                                              chloride    (89.5)                                                             m-(p-methoxycarbon-                                                            yl phenoxy)benzal                                                              chloride    (4.4)                                                              nucleus-substituted                                                                        (2.5)                                   ______________________________________                                    

EXAMPLES 37 TO 52

Table 4 shows the results of reactions which are conducted in a similar manner as in Example 20 with use of typical phenoxytoluene derivatives.

                  TABLE 4                                                          ______________________________________                                         Chlorination of phenoxytoluenes in the coexistence                             of N--diethyleneoxy-2-benzothiazolyl sulfenamide                                                  Reac.                                                       EX.  Starting material                                                                            time                (yield,                                 No.  (g)           (min.)  Products    %)                                      ______________________________________                                         37   m-phenoxytoluene                                                                             37      m-phenoxytoluene                                                                            (4.1)                                       (95)                  m-phenoxybenzyl                                                                chloride    (94.0)                                                             m-phenoxybenzal                                                                chloride    (1.5)                                                              nucleus-substituted                                                                        (0.4)                                   38   p-phenoxytoluene                                                                             76      p-phenoxybenzyl                                          (95)                  chloride    (4.2)                                                              p-phenoxybenzal                                                                chloride    (93.2)                                                             p-phenoxyphenyl                                                                trichloromethane                                                                           (1.8)                                                              nucleus-substituted                                                                        (0.8)                                   39   3-phenoxy-6-chloro-                                                                          88      3-phenoxy-6-chloro-                                      toluene               benzyl chloride                                                                            (4.7)                                        (114)                 3-phenoxy-6-chloro-                                                            benzal chloride                                                                            (92.8)                                                             3-phenoxy-6-chloro-                                                            phenyl trichloro-                                                              methane     (1.8)                                                              nucleus-substituted                                                                        (0.7)                                   40   m,m'-dimethyldi-                                                                             150     m,m'-di(chloro-                                          phenyl ether          methyl)diphenyl                                          (103)                 ether       (7.2)                                                              m,m'-di(dichloro-                                                              methyl)diphenyl                                                                ether       (88.7)                                                             m,m'-di(trichloro-                                                             methyl)diphenyl                                                                ether       (3.0)                                                              nucleus-substituted                                                                        (1.1)                                   41   m-(m-chloromethyl-                                                                           86      m-(m-chloromethyl-                                       phenoxy)toluene       phenoxy)toluene                                                                            (3.7)                                        (121)                 m-(m-dichloro-                                                                 methylphenoxy)                                                                 benzyl chloride                                                                            (92.4)                                                             m-(m-trichloro-                                                                methylphenoxy)                                                                 benzal chloride                                                                            (3.1)                                                              nucleus-substituted                                                                        (0.8)                                   42   m-(p-benzoylphen-                                                                            44      m-(p-benzoylphen-                                        oxy)toluene           oxy)toluene (5.7)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzyl chloride                                                                        (91.6)                                                             m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (2.2)                                                              nucleus-substituted                                                                        (0.5)                                   43   m-(p-benzoylphen-                                                                            80      m-(p-benzoylphen-                                        oxy)toluene           oxy)benzyl chloride                                                                        (3.0)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (94.9)                                                             m-(p-benzoylphen-                                                              oxy)phenyl tri-                                                                chloromethane                                                                              (1.3)                                                              nucleus-substituted                                                                        (0.8)                                   44   m-(p-cyanophenoxy)                                                                           87      m-(p-cyanophenoxy)-                                      toluene               benzyl chloride                                                                            (4.3)                                        (109)                 m-(p-cyanophenoxy)-                                                            benzal chloride                                                                            (92.0)                                                             m-(p-cyanophenoxy)-                                                            phenyl trichloro-                                                              methane     (2.5)                                                              nucleus-substituted                                                                        (1.2)                                   45   m-(p-nitrophenoxy)                                                                           90      m-(p-nitrophenoxy)-                                      toluene               benzyl chloride                                                                            (8.5)                                        (119)                 m-(p-nitrophenoxy)-                                                            benzal chloride                                                                            (88.1)                                                             m-(p-nitrophenoxy)-                                                            phenyl trichloro-                                                              methane     (2.0)                                                              nucleus-substituted                                                                        (1.4)                                   46   m-(p-phenylphen-                                                                             42      m-(p-phenylphen-                                         oxy)toluene           oxy)toluene (3.5)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzyl chloride                                                                        (93.7)                                                             m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (2.0)                                                              nucleus-substituted                                                                        (0.8)                                   47   m-(p-phenylphen-                                                                             84      m-(p-phenylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (1.1)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (95.8)                                                             m-(p-phenylphen-                                                               oxy)phenyl trichloro-                                                          methane     (2.0)                                                              nucleus-substituted                                                                        (1.1)                                   48   m-(p-benzylphen-                                                                             85      m-(p-benzylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (2.7)                                        (143)                 m-(p-benzylphen-                                                               oxy)benzal chloride                                                                        (94.9)                                                             m-(p-benzylphen-                                                               oxy)phenyl trichloro-                                                          methane     (1.5)                                                              nucleus-substituted                                                                        (0.9)                                   49   m-(p-benzyloxy-                                                                              82      m-(p-benzyloxy-                                          phenoxy)toluene       phenoxy)benzyl                                           (151)                 chloride    (3.5)                                                              m-(p-benzyloxy-                                                                phenoxy)benzal                                                                 chloride    (94.0)                                                             m-(p-benzyloxy-                                                                phenoxy)phenyl                                                                 trichloromethane                                                                           (1.8)                                                              nucleus-substituted                                                                        (0.7)                                   50   p-(m-tolyloxy)                                                                               85      p-(m-chloromethyl-                                       phenyl benzoate       phenoxy)phenyl                                           (158)                 benzoate    (2.0)                                                              p-(m-dichloro-                                                                 methylphenoxy)-                                                                phenyl benzoate                                                                            (95.6)                                                             p-(m-trichloro-                                                                methylphenoxy)-                                                                phenyl benzoate                                                                            (1.9)                                                              nucleus-substituted                                                                        (0.5)                                   51   m-(p-methoxyphen-                                                                            40      m-(p-methoxyphen-                                        oxy)toluene           oxy)toluene (3.6)                                        (111)                 m-(p-methoxyphen-                                                              oxy)benzyl chloride                                                                        (91.0)                                                             m-(p-methoxyphen-                                                              oxy)benzal chloride                                                                        (4.1)                                                              nucleus-substituted                                                                        (1.3)                                   52   m-(p-methoxycar-                                                                             40      m-(p-methoxycarbon-                                      bonyl phenoxy)-       yl phenoxy)toluene                                                                         (4.8)                                        toluene               m-(p-methoxycarbon-                                      (126)                 yl phenoxy)benzyl                                                              chloride    (90.4)                                                             m-(p-methoxycarbon-                                                            yl phenoxy)benzal                                                              chloride    (3.2)                                                              nucleus-substituted                                                                        (1.6)                                   ______________________________________                                    

EXAMPLE 53

Table 5 shows the results of reactions which are conducted in a similar manner as in Example 19 with use of m-phenoxytoluene and typical sulfur-containing compounds.

                                      TABLE 5                                      __________________________________________________________________________     Effect of sulfur-containing compounds on the                                   chlorination of m-phenoxytoluene                                                                    Reac.                                                     Sulfur-containing    time                                                                               Products (Yield, %)                                   No. compound         (min.)                                                                             (1)                                                                              (2)                                                                               (3)                                                                               (4)                                                                              (5)                                         __________________________________________________________________________     1   Methyl cyclohexyl                                                                               70  --                                                                               6.7                                                                               89.0                                                                              3.1                                                                              1.2                                             thioketone                                                                 2   4,4'-Bis(N,Ndimethyl-                                                                           70  --                                                                               3.5                                                                               90.8                                                                              3.9                                                                              1.8                                             amino)thiobenzophenone                                                     3   1-Isopropyl-3-(n-dodecyl)-                                                                      35  3.8                                                                              90.8                                                                              4.4                                                                               --                                                                               1.0                                             2-thiourea                                                                 4   1-Isopropyl-3-(n-dodecyl)-                                                                      75  --                                                                               2.4                                                                               93.5                                                                              2.8                                                                              1.3                                             2-thiourea                                                                 5   1-(p-Tolyl)-3-(2-pyridyl)-                                                                      75  --                                                                               3.4                                                                               93.8                                                                              1.6                                                                              1.2                                             2-thiourea                                                                 6   1,1,3,3-Tetra-n-propyl-                                                                         75  --                                                                               3.9                                                                               91.7                                                                              3.4                                                                              1.0                                             2-thiourea                                                                 7   1,4-Diethyl-1,4-diphenyl-                                                                       75  --                                                                               4.1                                                                               92.1                                                                              2.7                                                                              1.1                                             3-thiosemicarbazide                                                        8   1-Isonicotinoyl-4-(n-octa-                                                                      75  --                                                                               3.3                                                                               93.4                                                                              2.0                                                                              1.3                                             decanoyl)-3-thiosemi-                                                          carbazide                                                                  9   1-(n-Heptadecyl)-4-                                                                             75  --                                                                               3.8                                                                               92.2                                                                              3.1                                                                              0.9                                             thiosemicarbazone                                                          10  1-Pentamethylene-4-                                                                             35  3.9                                                                              90.3                                                                              4.6                                                                               --                                                                               1.2                                             thiosemicarbazone                                                          11  1-Pentamethylene-4-                                                                             75  --                                                                               2.4                                                                               93.7                                                                              2.4                                                                              1.5                                             thiosemicarbazone                                                          12  1,5-Diphenyl-3-  75  --                                                                               3.1                                                                               92.9                                                                              2.1                                                                              1.9                                             thiocarbohydrazide                                                         13  Dithizone        75  --                                                                               4.6                                                                               91.9                                                                              1.7                                                                              1.8                                         14  1,7-Di-n-heptadecyl-4-                                                                          75  --                                                                               4.0                                                                               92.4                                                                              2.5                                                                              1.1                                             bisthiocarbohydrazone                                                      15  1,7-Dipentamethylene-                                                                           75  --                                                                               2.6                                                                               93.5                                                                              2.9                                                                              1.0                                             4-bisthiocarbohydrazone                                                    16  5-Ethyl-2-thiobiuret                                                                            73  --                                                                               4.0                                                                               90.4                                                                              3.5                                                                              2.1                                         17  5-(n-Propyl)-2,4-                                                                               75  --                                                                               2.8                                                                               92.3                                                                              3.0                                                                              1.9                                             dithiobiuret                                                               18  N,N',N",N'"Hexamethylguanyl                                                                     70  --                                                                               5.0                                                                               89.0                                                                              3.9                                                                              2.1                                             thiourea                                                                   19  n-Heptadecylthioamide                                                                           75  --                                                                               5.8                                                                               90.1                                                                              2.8                                                                              1.3                                         20  NCyclohexylthiobenzamide                                                                        75  --                                                                               4.8                                                                               90.9                                                                              3.1                                                                              1.2                                         21  2-Benzothiazolylethyl                                                                           75  --                                                                               5.0                                                                               91.7                                                                              2.2                                                                              1.1                                             thioanilide                                                                22  Thiophenylacetohydrazide                                                                        80  --                                                                               5.1                                                                               88.7                                                                              2.9                                                                              3.3                                         23  2,4-Dichlorophenyl                                                                              75  --                                                                               4.3                                                                               90.3                                                                              2.4                                                                              3.0                                             thiophenylacetohydrazone                                                   24  N(n-Octyl)-Naminoethyl                                                                          75  --                                                                               4.1                                                                               93.4                                                                              1.3                                                                              1.2                                             dithiocarbamic acid                                                        25  2-Thiazolyldithiocarbamic                                                                       34  1.2                                                                              94.0                                                                              3.8                                                                               --                                                                               1.0                                             acid triethylammonium salt                                                 26  2-Thiazolyldithiocarbamic                                                                       75  --                                                                               1.3                                                                               95.6                                                                              2.0                                                                              1.1                                             acid triethylammonium salt                                                 27  Cyclohexyldithiocarbamic                                                                        74  --                                                                               4.4                                                                               90.8                                                                              3.1                                                                              1.7                                             acid cyclohexylammonium                                                        salt                                                                       28  N,NDimethyl S(n-hexa-                                                                           75  --                                                                               3.3                                                                               91.8                                                                              2.9                                                                              2.0                                             decyl)dithiocarbamate                                                      29  N,NDimethyl S(2-benzo-                                                                          35  2.6                                                                              93.6                                                                              2.9                                                                               --                                                                               0.9                                             thiazolyl)dithiocarbamate                                                  30  N,NDimethyl S(2-benzo-                                                                          75  --                                                                               2.1                                                                               94.4                                                                              1.4                                                                              2.1                                             thiazolyl)dithiocarbamate                                                  31  NPentamethylene S                                                                               80  --                                                                               5.1                                                                               92.7                                                                              1.0                                                                              1.2                                             mercaptoethyl dithio-                                                          carbamate                                                                  32  NDiethyleneoxy Shy-                                                                             77  --                                                                               5.7                                                                               91.8                                                                              1.2                                                                              1.3                                             droxyethyl dithiocarbamate                                                 33  NCarboxymethyl O(η-hexa-                                                                    75  --                                                                               7.1                                                                               90.0                                                                              1.8                                                                              1.1                                             decyl) thioncarbamate                                                      34  NPentamethylene O(n-                                                                            75  --                                                                               6.6                                                                               89.1                                                                              3.1                                                                              1.2                                             propyl) thioncarbamate                                                     35  Diethyl dithiocarbamyl                                                                          78  --                                                                               3.8                                                                               92.4                                                                              2.1                                                                              1.7                                             sulfenamide                                                                36  Benzyl thionpropionate                                                                          75  --                                                                               4.1                                                                               88.7                                                                              4.1                                                                              3.1                                         37  Isoamyl p-thiontoluate                                                                          75  --                                                                               6.1                                                                               87.9                                                                              3.8                                                                              2.2                                         38  Dithiobenzoic acid                                                                              85  --                                                                               2.0                                                                               90.2                                                                              4.7                                                                              3.1                                         39  Ethyl dithio-n-heptanoate                                                                       76  --                                                                               3.4                                                                               90.1                                                                              3.7                                                                              2.8                                         40  n-Buthyl dithiocyclo-                                                                           75  --                                                                               3.5                                                                               90.0                                                                              4.0                                                                              2.5                                             hexanecarboxylate                                                          41  n-Dodecyl phenylthion-                                                                          75  --                                                                               7.4                                                                               89.3                                                                              2.1                                                                              1.2                                             carbonate                                                                  42  Tetramethylenethion-                                                                            75  --                                                                               3.9                                                                               92.1                                                                              3.0                                                                              1.0                                             carbonate                                                                  43  Di-n-octadecyl trithio-                                                                         78  --                                                                               4.9                                                                               91.8                                                                              1.9                                                                              1.4                                             carbonate                                                                  44  Di-n-dodecyl trithio-                                                                           76  --                                                                               5.6                                                                               90.2                                                                              2.2                                                                              2.0                                             carbonate                                                                  45  Dicyclohexyl trithio-                                                                           76  --                                                                               5.4                                                                               90.7                                                                              2.0                                                                              1.9                                             carbonate                                                                  46  S,O(di-n-dodecyl)-                                                                              75  --                                                                               4.1                                                                               91.2                                                                              3.4                                                                              1.3                                             xanthate                                                                   47  Scarboxydecamethylene                                                                           75  --                                                                               5.3                                                                               90.9                                                                              2.8                                                                              1.0                                             O(n-dodecyl)xanthate                                                       48  S(n-hexadecyl) Ocyclo-                                                                          75  --                                                                               5.4                                                                               90.3                                                                              3.1                                                                              1.2                                             hexyl xanthate                                                             49  1-(n-dodecylidene)                                                                              75  --                                                                               5.0                                                                               91.9                                                                              1.9                                                                              1.2                                             Oethylthioncarbazate                                                       50  1-(n-dodecylidene)                                                                              75  --                                                                               3.1                                                                               93.4                                                                              2.2                                                                              1.3                                             Sethyldithiocarbazate                                                      51  Cyclohexyl isothiocyanate                                                                       75  --                                                                               6.3                                                                               88.1                                                                              3.9                                                                              1.7                                         52  p-(N,Ndimethylamino)-                                                                           76  --                                                                               5.2                                                                               90.0                                                                              3.0                                                                              1.8                                             phenyl isothiocyanate                                                      53  6-Isothiocyanoquinoline                                                                         75  --                                                                               3.9                                                                               90.8                                                                              3.2                                                                              2.1                                         54  Hexamethylene diiso-                                                                            35  5.1                                                                              88.9                                                                              5.0                                                                               --                                                                               1.0                                             thiocyanate                                                                55  Hexamethylene diiso-                                                                            75  --                                                                               6.4                                                                               89.0                                                                              3.5                                                                              1.1                                             thiocyanate                                                                56  Methylenebistetramethylene                                                                      75  --                                                                               5.4                                                                               91.3                                                                              2.1                                                                              1.2                                             thiourea                                                                   57  Bis(Ntrimethylenethio-                                                                          75  --                                                                               4.1                                                                               90.8                                                                              3.1                                                                              2.0                                             acetamide)                                                                 58  Ethylenebisdithiocarbamic                                                                       80  --                                                                               1.7                                                                               96.0                                                                              1.2                                                                              1.1                                             acid diammonium salt                                                       59  O,O'dicyclohexyl S,S'                                                                           77  --                                                                               4.3                                                                               92.4                                                                              2.3                                                                              1.0                                             methylenebisxanthate                                                       60  Cyclohexylxanthogene-                                                                           75  --                                                                               3.8                                                                               92.9                                                                              2.1                                                                              1.2                                             monosulfide                                                                61  n-Hexadecyl dixanthogene                                                                        76  --                                                                               2.7                                                                               93.4                                                                              2.8                                                                              1.1                                         62  Benzyl dixanthogene                                                                             75  --                                                                               2.2                                                                               94.1                                                                              2.7                                                                              1.0                                         63  Ethyl dixanthogene                                                                              78  --                                                                               1.5                                                                               95.6                                                                              1.8                                                                              1.1                                             disulfide                                                                  64  N,N'dimorpholino 80  --                                                                               2.6                                                                               90.9                                                                              4.1                                                                              2.4                                             dithiooxalic diamide                                                       65  Bis(piperidinothio-                                                                             75  --                                                                               4.0                                                                               91.7                                                                              2.3                                                                              2.0                                             carbonyl) monosulfide                                                      66  Bis(morpholinothio-                                                                             75  --                                                                               3.1                                                                               92.9                                                                              2.1                                                                              1.9                                             carbonyl) monosulfide                                                      67  Bis(piperidinothio-                                                                             75  --                                                                               2.3                                                                               93.8                                                                              2.0                                                                              1.9                                             carbonyl) disulfide                                                        68  Bis(morpholinothio-                                                                             75  --                                                                               2.1                                                                               94.1                                                                              2.0                                                                              1.8                                             carbonyl) disulfide                                                        69  Ethylene-1,2-bis[1,2-                                                                           78  --                                                                               1.9                                                                               92.7                                                                              3.4                                                                              2.0                                             (dithiocarbamoyl)-                                                             ethylene] disulfide                                                        70  Bis(piperidinothio-                                                                             80  --                                                                               1.2                                                                               94.8                                                                              1.9                                                                              2.1                                             carbonyl) hexasulfide                                                      71  Pentamethylene   75  --                                                                               7.4                                                                               89.5                                                                              1.2                                                                              1.9                                             dithiocyanate                                                              72  3-Thiocyanopyridine                                                                             38  2.8                                                                              87.5                                                                              8.3                                                                               --                                                                               1.4                                         73  3-Thiocyanopyridine                                                                             75  --                                                                               5.7                                                                               90.2                                                                              1.3                                                                              2.8                                         74  N(n-Heptadecyl)-n-octyl                                                                         75  --                                                                               3.4                                                                               93.5                                                                              2.4                                                                              0.7                                             sulfenamide                                                                75  Tert-Butylethyl  75  --                                                                               5.0                                                                               90.2                                                                              2.3                                                                              2.5                                             thiosulfinate                                                              76  Thiostearic acid 80  --                                                                               4.2                                                                               91.7                                                                              1.0                                                                              3.1                                         77  Dicyclohexyldithiol                                                                             75  --                                                                               5.0                                                                               91.1                                                                              2.2                                                                              1.7                                             sebacate                                                                   78  S,S'Dimethylenecarboxy                                                                          75  --                                                                               11.3                                                                              86.4                                                                              1.1                                                                              1.2                                             O,O'diethylbisthiol                                                            carbonate                                                                  79  Diisoamyldithiol 75  --                                                                               7.2                                                                               89.5                                                                              1.7                                                                              1.6                                             carbonate                                                                  80  N(ζ-Aminohexamethyl)                                                                       80  --                                                                               4.3                                                                               91.8                                                                              1.1                                                                              2.8                                             thiocarbamic acid                                                          81  NStearylthiocarbamic                                                                            35  4.5                                                                              92.5                                                                              1.9                                                                               --                                                                               1.1                                             acid stearylammonium                                                           salt                                                                       82  NStearylthiocarbamic                                                                            75  --                                                                               1.1                                                                               95.1                                                                              1.8                                                                              2.0                                             acid stearylammonium                                                           salt                                                                       83  NPentamethylene Sphenyl                                                                         75  --                                                                               1.8                                                                               94.5                                                                              1.9                                                                              1.8                                             thiol carbamate                                                            84  2-Thienylmercapto-                                                                              80  --                                                                               4.7                                                                               90.3                                                                              2.6                                                                              2.4                                             acetic acid                                                                85  n-Octadecylmercapto-                                                                            75  --                                                                               8.1                                                                               89.8                                                                              1.0                                                                              1.1                                             succinic acid diethyl                                                          ester                                                                      86  Methylmercaptopelargonic                                                                        80  --                                                                               2.6                                                                               92.7                                                                              1.9                                                                              2.8                                             acid amide                                                                 87  S,S'Di(n-octadecyl)methyl                                                                       75  --                                                                               10.9                                                                              85.4                                                                              1.6                                                                              2.1                                             thioacetal                                                                 88  S,S'Dibenzylcyclohexyl                                                                          76  --                                                                               8.5                                                                               88.4                                                                              1.9                                                                              1.2                                             ketone thioacetal                                                          89  Tri-n-dodecyl trithio-                                                                          75  --                                                                               8.0                                                                               87.2                                                                              2.1                                                                              2.7                                             orthoformate                                                               90  Tetracyclohexyl tetra-                                                                          75  --                                                                               6.5                                                                               89.0                                                                              2.4                                                                              2.1                                             thioorthocarbonate                                                         91  1,10-Decamethylenebis-                                                                          73  --                                                                               5.2                                                                               91.2                                                                              1.0                                                                              2.6                                             chloroethyl sulfide                                                        92  Di(Npentamethyleneamino-                                                                        35  3.9                                                                              92.6                                                                              2.6                                                                               --                                                                               0.9                                             ethyl) sulfide                                                             93  Di(Npentamethyleneamino-                                                                        75  --                                                                               3.5                                                                               93.4                                                                              1.1                                                                              2.0                                             ethyl) sulfide                                                             94  p-Benzylmercapto-                                                                               75  --                                                                               7.7                                                                               89.0                                                                              1.1                                                                              2.2                                             benzaldehyde                                                               95  n-Dodecylmercaptomethyl                                                                         75  --                                                                               7.0                                                                               89.7                                                                              1.6                                                                              1.7                                             phenyl ketone                                                              96  n-Octadecylmercapto-                                                                            78  --                                                                               9.7                                                                               86.3                                                                              2.2                                                                              1.8                                             propionitrile                                                              97  Dibenzoyl sulfide                                                                               75  --                                                                               5.6                                                                               90.0                                                                              2.1                                                                              2.3                                         98  Bis{2-[2-(2-chloroethyl-                                                                        83  --                                                                               3.8                                                                               93.4                                                                              1.7                                                                              1.1                                             thio)ethylthio]ethyl}                                                          sulfide                                                                    99  Poly(ethylenesulfide)                                                                           75  --                                                                               4.1                                                                               92.6                                                                              2.3                                                                              1.0                                             --Mn = 1,100                                                               100 Di(κ-carboxydecyl)disulfide                                                               76  --                                                                               4.6                                                                               91.2                                                                              3.1                                                                              1.1                                         101 Di(cyclohexyloxycarbonyl-                                                                       75  --                                                                               4.9                                                                               91.7                                                                              2.1                                                                              1.3                                             ethyl)disulfide                                                            102 Di(Nmethylanilinocarbonyl-                                                                      35  4.1                                                                              90.3                                                                              4.5                                                                               --                                                                               1.1                                             methyl)disulfide                                                           103 Di(Nmethylanilinocarbonyl-                                                                      75  --                                                                               2.8                                                                               94.0                                                                              1.3                                                                              1.9                                             methyl)disulfide                                                           104 Di(2,4-dichlorophenyl)                                                                          75  --                                                                               5.0                                                                               92.0                                                                              1.9                                                                              1.1                                             disulfide                                                                  105 Di(N,Ndimethylamino-                                                                            80  --                                                                               4.2                                                                               92.3                                                                              2.1                                                                              1.4                                             hexamethyl)disulfide                                                       106 Di(o-formylmethylthio-                                                                          78  --                                                                               5.7                                                                               90.6                                                                              1.6                                                                              2.1                                             phenyl)disulfide                                                           107 Di(methylcarbonyl-                                                                              75  --                                                                               6.5                                                                               90.3                                                                              2.0                                                                              1.2                                             isobutyl)disulfide                                                         108 ζ-Cyano-ζ'-hydroxy                                                                    78  --                                                                               8.1                                                                               87.3                                                                              2.9                                                                              1.7                                             dihexamethyl disulfide                                                     109 Di-3-nicotinoyl disulfide                                                                       38  9.2                                                                              87.1                                                                              2.4                                                                               --                                                                               1.3                                         110 Di-3-nicotinoyl disulfide                                                                       78  --                                                                               8.3                                                                               88.5                                                                              2.1                                                                              1.1                                         111 Poly(ethylformal disulfide)                                                                     75  --                                                                               4.5                                                                               92.1                                                                              1.3                                                                              2.1                                             --Mn = 2,400                                                               112 Poly(ethylene disulfide)                                                                        75  --                                                                               3.1                                                                               93.8                                                                              1.1                                                                              2.0                                             --Mn = 500                                                                 113 Di(γ-hydroxypropyl)                                                                       76  --                                                                               5.7                                                                               90.2                                                                              2.7                                                                              1.4                                             disulfide                                                                  114 Di(2-ethoxy-1-naphthyl)                                                                         77  --                                                                               4.5                                                                               90.7                                                                              2.2                                                                              2.6                                             disulfide                                                                  115 Di(carboxymethyl)                                                                               78  --                                                                               5.1                                                                               90.5                                                                              1.7                                                                              2.7                                             trisulfide                                                                 116 Di(p-ethoxycarbonyl-                                                                            75  --                                                                               5.4                                                                               91.5                                                                              1.8                                                                              1.3                                             phenyl)trisulfide                                                          117 Di(o-n-butylcarbamoyl-                                                                          78  --                                                                               4.7                                                                               92.3                                                                              1.2                                                                              1.8                                             phenyl)tetrasulfide                                                        118 Di(β-chloroethyl)                                                                          35  6.4                                                                              90.1                                                                              2.1                                                                               --                                                                               1.4                                             pentasulfide                                                               119 Di(β-chloroethyl)                                                                          75  --                                                                               2.9                                                                               92.7                                                                              1.6                                                                              2.8                                             pentasulfide                                                               120 Di(ethylenediamino-                                                                             78  --                                                                               5.5                                                                               90.3                                                                              1.9                                                                              2.3                                             ethyl)tetrasulfide                                                         121 Di(β-formylethyl)                                                                          76  --                                                                               6.6                                                                               89.8                                                                              1.7                                                                              1.9                                             trisulfide                                                                 122 Di(acetylmethyl) 75  --                                                                               7.7                                                                               88.1                                                                              2.2                                                                              2.0                                             trisulfide                                                                 123 Di(β-cyanoethyl)                                                                           75  --                                                                               9.1                                                                               87.9                                                                              1.8                                                                              1.2                                             trisulfide                                                                 124 Dibenzoyl tetrasulfide                                                                          36  6.5                                                                              88.2                                                                              3.4                                                                               --                                                                               1.9                                         125 Dibenzoyl tetrasulfide                                                                          75  --                                                                               5.4                                                                               90.3                                                                              1.8                                                                              2.5                                         126 Poly(ethyl ether tetra-                                                                         75  --                                                                               2.6                                                                               93.4                                                                              1.1                                                                              2.9                                             sulfide)                                                                       --Mn = 1,100                                                               127 Di(2-hydroxy-1-naphthyl)                                                                        80  --                                                                               7.5                                                                               87.1                                                                              4.3                                                                              1.1                                             trisulfide                                                                 128 Di(2-ethoxy-1-naphthyl)                                                                         75  --                                                                               6.2                                                                               88.7                                                                              2.1                                                                              3.0                                             trisulfide                                                                 129 κ-Mercaptoundecylic acid                                                                  85  --                                                                               4.8                                                                               91.2                                                                              1.7                                                                              2.3                                         130 Mercaptosuccinic acid                                                                           84  --                                                                               3.8                                                                               92.3                                                                              1.6                                                                              2.3                                             ethyl ester                                                                131 ε-Mercaptocaproic                                                                       90  --                                                                               3.4                                                                               90.7                                                                              2.8                                                                              3.1                                             acid amide                                                                 132 Pentachlorothiophenol                                                                           78  --                                                                               3.9                                                                               90.8                                                                              2.8                                                                              2.5                                         133 N,N'Di(γ-mercaptoiso-                                                                     88  --                                                                               2.7                                                                               93.4                                                                              1.1                                                                              2.8                                             butyl)piperazine                                                           134 β-Formylethyl mercaptan                                                                    85  --                                                                               4.1                                                                               90.9                                                                              2.6                                                                              2.4                                         135 Di(p-mercaptophenyl)                                                                            90  --                                                                               3.9                                                                               92.3                                                                              1.5                                                                              2.3                                             ketone                                                                     136 β-Cyanoethyl mercaptan                                                                     80  --                                                                               3.2                                                                               89.8                                                                              3.4                                                                              3.6                                         137 Bis(ethylenedimercapto-                                                                         90  --                                                                               3.3                                                                               92.7                                                                              1.6                                                                              2.4                                             methyl) methane                                                            138 Di(β-mercaptoethyl)                                                                        83  --                                                                               3.5                                                                               91.4                                                                              2.4                                                                              2.7                                             disulfide                                                                  139 Di(β-mercaptoethyl)                                                                        85  --                                                                               3.6                                                                               93.2                                                                              1.2                                                                              2.0                                             tetrasulfide                                                               140 1,6-Hexamethylene dithiol                                                                       85  --                                                                               4.1                                                                               92.3                                                                              1.9                                                                              1.7                                         __________________________________________________________________________      ##STR13##                                                                                                                                                     ##STR14##                                                                                                                                                     ##STR15##                                                                      ##STR16##                                                                                                                                                     ##STR17##                                                                                                                                               

EXAMPLE 54

The procedure of Example 1 is followed with use of 95 g (0.52 mole) of m-phenoxytoluene, 10 g of azobisisobutyronitrile, 1 g of triphenylphosphine and 1,300 g of carbon tetrachloride. The reaction time is 75 minutes. Analysis of the product by gas chromatography shows 4.9% of m-phenoxybenzyl chloride, 90.1% of m-phenoxybenzal chloride, 4.2% of m-phenoxyphenyl trichloromethane and 0.8% of nuclear-chlorinated compounds. For comparison, the same reaction is conducted, except that the above triphenylphosphine is not used. The result shows 41.0% of m-phenoxytoluene, 45.7% of m-phenoxbenzyl chloride, 12.1% of m-phenoxybenzal chloride and 1.2% of nuclear-chlorinated compounds.

EXAMPLES 55 TO 70

Chlorination reactions are carried out in a similar manner as in Example 54 with use of typical phenoxytoluene derivatives listed in Table 6. The results are also given in Table.

                  TABLE 6                                                          ______________________________________                                         Chlorination of phenoxytoluenes in the coexistence                             of triphenylphosphine                                                                             Reac.                                                            Starting material                                                                            time                (yield,                                 No.  (g)           (min.)  Products    %)                                      ______________________________________                                         55   m-phenoxytoluene                                                                             40      m-phenoxytoluene                                                                            (4.4)                                       (95)                  m-phenoxybenzyl                                                                chloride    (90.3)                                                             m-phenoxybenzal                                                                chloride    (4.8)                                                              nucleus-substituted                                                                        (0.5)                                   56   p-phenoxytoluene                                                                             80      p-phenoxybenzyl                                          (95)                  chloride    (4.2)                                                              p-phenoxybenzal                                                                chloride    (91.5)                                                             p-phenoxyphenyl                                                                trichloromethane                                                                           (3.4)                                                              nucleus-substituted                                                                        (0.9)                                   57   3-phenoxy-6-chloro-                                                                          90      3-phenoxy-6-chloro-                                      toluene               benzyl chloride                                                                            (8.9)                                        (114)                 3-phenoxy-6-chloro-                                                            benzal chloride                                                                            (87.6)                                                             3-phenoxy-6-chloro-                                                            phenyl trichloro-                                                              methane     (2.5)                                                              nucleus-substituted                                                                        (1.0)                                   58   m,m'-dimethyldi-                                                                             160     m,m'-di(chloro-                                          phenyl ether          methyl)diphenyl                                          (103)                 ether       (11.7)                                                             m,m'-di(dichloro-                                                              methyl)diphenyl                                                                ether       (80.9)                                                             m,m'-di(trichloro-                                                             methyl)diphenyl                                                                ether       (4.9)                                                              nucleus-substituted                                                                        (2.5)                                   59   m-(m-chloromethyl-                                                                           90      m-(m-chloromethyl-                                       phenoxy)toluene       phenoxy)toluene                                                                            (12.6)                                       (121)                 m-(m-dichloro-                                                                 methylphenoxy)                                                                 benzyl chloride                                                                            (82.3)                                                             m-(m-trichloro-                                                                methylphenoxy)                                                                 benzal chloride                                                                            (3.1)                                                              nucleus-substituted                                                                        (2.0)                                   60   m-(p-benzoylphen-                                                                            40      m-(p-benzoylphen-                                        oxy)toluene           oxy)toluene (4.9)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzyl chloride                                                                        (90.6)                                                             m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (3.5)                                                              nucleus-substituted                                                                        (1.0)                                   61   m-(p-benzoylphen-                                                                            80      m-(p-benzoylphen-                                        oxy)toluene           oxy)benzyl chloride                                                                        (2.8)                                        (150)                 m-(p-benzoylphen-                                                              oxy)benzal chloride                                                                        (92.7)                                                             m-(p-benzoylphen-                                                              oxy)phenyl tri-                                                                chloromethane                                                                              (3.0)                                                              nucleus-substituted                                                                        (1.5)                                   62   m-(p-cyanophenoxy)                                                                           80      m-(p-cyanophenoxy)-                                      toluene               benzyl chloride                                                                            (8.2)                                        (109)                 m-(p-cyanophenoxy)-                                                            benzal chloride                                                                            (85.6)                                                             m-(p-cyanophenoxy)-                                                            phenyl trichloro-                                                              methane     (3.9)                                                              nucleus-substituted                                                                        (2.3)                                   63   m-(p-nitrophenoxy)                                                                           90      m-(p-nitrophenoxy)-                                      toluene               benzyl chloride                                                                            (12.0)                                       (119)                 m-(p-nitrophenoxy)-                                                            benzal chloride                                                                            (80.5)                                                             m-(p-nitrophenoxy)-                                                            phenyl trichloro-                                                              methane     (4.3)                                                              nucleus-substituted                                                                        (3.2)                                   64   m-(p-phenylphen-                                                                             40      m-(p-phenylphen-                                         oxy)toluene           oxy)toluene (3.2)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzyl chloride                                                                        (93.5)                                                             m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (2.1)                                                              nucleus-substituted                                                                        (1.2)                                   65   m-(p-phenylphen-                                                                             90      m-(p-phenylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (1.1)                                        (135)                 m-(p-phenylphen-                                                               oxy)benzal chloride                                                                        (93.0)                                                             m-(p-phenylphen-                                                               oxy)phenyl trichloro-                                                          methane     (4.8)                                                              nucleus-substituted                                                                        (1.1)                                   66   m-(p-benzylphen-                                                                             90      m-(p-benzylphen-                                         oxy)toluene           oxy)benzyl chloride                                                                        (4.9)                                        (143)                 m-(p-benzylphen-                                                               oxy)benzal chloride                                                                        (90.5)                                                             m-(p-benzylphen-                                                               oxy)phenyl trichloro-                                                          methane     (3.8)                                                              nucleus-substituted                                                                        (0.8)                                   67   m-(p-benzyloxy-                                                                              90      m-(p-benzyloxy-                                          phenoxy)toluene       phenoxy)benzyl                                           (151)                 chloride    (5.5)                                                              m-(p-benzyloxy-                                                                phenoxy)benzal                                                                 chloride    (88.7)                                                             m-(p-benzyloxy-                                                                phenoxy)phenyl                                                                 trichloromethane                                                                           (4.3)                                                              nucleus-substituted                                                                        (1.5)                                   68   p-(m-tolyloxy)                                                                               80      p-(m-chloromethyl-                                       phenyl benzoate       phenoxy)phenyl                                           (158)                 benzoate    (2.7)                                                              p-(m-dichloro-                                                                 methylphenoxy)-                                                                phenyl benzoate                                                                            (90.9)                                                             p-(m-trichloro-                                                                methylphenoxy)-                                                                phenyl benzoate                                                                            (4.5)                                                              nucleus-substituted                                                                        (1.9)                                   69   m-(p-methoxyphen-                                                                            40      m-(p-methoxyphen-                                        oxy)toluene           oxy)toluene (8.4)                                        (111)                 m-(p-methoxyphen-                                                              oxy)benzyl chloride                                                                        (87.1)                                                             m-(p-methoxyphen-                                                              oxy)benzal chloride                                                                        (3.5)                                                              nucleus-substituted                                                                        (1.0)                                   70   m-(p-methoxycar-                                                                             40      m-(p-methoxycarbon-                                      bonyl phenoxy)-       yl phenoxy)toluene                                                                         (6.9)                                        toluene               m-(p-methoxycarbon-                                      (126)                 yl phenoxy)benzyl                                                              chloride    (86.7)                                                             m-(p-methoxycarbon-                                                            yl phenoxy)benzal                                                              chloride    (4.2)                                                              nucleus-substituted                                                                        (2.2)                                   ______________________________________                                    

EXAMPLE 71

Table 7 shows the results of reactions which are conducted in a similar manner as in Example 54 with use of m-phenoxytoluene and typical phosphorus- or oxygen-containing compounds.

                                      TABLE 7                                      __________________________________________________________________________     Effect of phosphorus-containing and oxygen-containing                          compounds on the chlorination of m-phenoxytoluene                              Phosphorus-containing                                                                             Reac.                                                       or oxygen-containing                                                                              time                                                                               Products (Yield, %)                                     No. compound       (min.)                                                                             (1)                                                                               (2)                                                                               (3)                                                                               (4)                                                                               (5)                                         __________________________________________________________________________     1   Tri-n-butylphosphine                                                                          40   9.3                                                                              89.1                                                                              1.1                                                                               -- 0.5                                         2   Tri-n-butylphosphine                                                                          75  -- 8.6                                                                               90.0                                                                              1.0                                                                               0.4                                         3   Tri-n-octylphosphine                                                                          80  -- 8.2                                                                               89.2                                                                              1.6                                                                               1.0                                         4   Tri-n-dodecylphosphine                                                                        80  -- 5.3                                                                               91.8                                                                              2.9                                                                               --                                          5   n-Octadecyldiphenyl-                                                                          80  -- 5.5                                                                               92.4                                                                              1.2                                                                               0.9                                             phosphine                                                                  6   Mercaptoethyldiphenyl                                                                         85  -- 4.7                                                                               89.8                                                                              3.3                                                                               2.2                                             phosphine                                                                  7   Tricyclohexylphosphine                                                                        80  -- 5.9                                                                               90.7                                                                              2.4                                                                               1.0                                         8   Dicyclohexyl 4-chloro-                                                                        75  -- 7.5                                                                               91.0                                                                              1.5                                                                               --                                              phenylphosphine                                                            9   Triisopropylphosphine                                                                         80  -- 5.8                                                                               89.3                                                                              4.2                                                                               0.7                                             sulfide                                                                    10  n-Hexadecyldiphenyl-                                                                          40  10.1                                                                              88.6                                                                              1.3                                                                               -- --                                              phosphine sulfide                                                          11  n-Hexadecyldiphenyl-                                                                          80  -- 4.5                                                                               90.8                                                                              3.2                                                                               1.5                                             phosphine sulfide                                                          12  Triphenylphosphine oxide                                                                      80  -- 7.8                                                                               87.5                                                                              3.5                                                                               1.2                                         13  Tri-n-dodecylphosphine                                                                        80  -- 4.8                                                                               92.6                                                                              2.6                                                                               --                                              oxide                                                                      14  N,NDiethylhydrazino-                                                                          80  -- 7.7                                                                               90.3                                                                              1.5                                                                               0.5                                             diphenylphosphine oxide                                                    15  1-Phenyl-1-phosphacyclo-                                                                      80  -- 5.2                                                                               91.1                                                                              3.1                                                                               0.6                                             hexane                                                                     16  n-Octadecyl diphenyl                                                                          80  -- 3.9                                                                               89.8                                                                              4.8                                                                               1.5                                             phosphite                                                                  17  Dicyclohexyl chloro                                                                           80  -- 2.9                                                                               91.9                                                                              4.0                                                                               1.2                                             phosphite                                                                  18  Di-n-octyl phosphite                                                                          40  11.3                                                                              78.5                                                                              10.2                                                                              -- --                                          19  Di-n-octyl phosphite                                                                          80  -- 10.3                                                                              85.2                                                                              3.5                                                                               1.0                                         20  Diphenyl cyclohexyl                                                                           80  -- 8.8                                                                               89.1                                                                              2.1                                                                               --                                              phosphite                                                                  21  Triphenyl phosphite                                                                           45   7.7                                                                              80.6                                                                              10.7                                                                              -- 1.0                                         22  Triphenyl phosphite                                                                           80  -- 5.0                                                                               91.7                                                                              3.3                                                                               --                                          23  Tricyclohexyl phosphite                                                                       75  -- 8.1                                                                               85.3                                                                              4.5                                                                               2.1                                         24  Diisopropyl chloro                                                                            80  -- 12.5                                                                              83.9                                                                              2.1                                                                               1.5                                             thiophosphite                                                              25  Tricyclohexyl thiophosphite                                                                   80  -- 7.0                                                                               87.6                                                                              4.1                                                                               1.3                                         26  Tri-n-dodecyl thiophosphite                                                                   80  -- 6.4                                                                               90.9                                                                              2.7                                                                               --                                          27  Triphenyl thiophosphite                                                                       45  15.3                                                                              80.5                                                                              4.2                                                                               -- --                                          28  Triphenyl thiophosphite                                                                       80  -- 4.8                                                                               90.5                                                                              4.7                                                                               --                                          29  Tris(dimethylamino)-                                                                          80  -- 7.4                                                                               87.6                                                                              1.9                                                                               3.1                                             phosphine                                                                  30  Phosphorus tripiperidide                                                                      80  -- 8.1                                                                               89.9                                                                              2.0                                                                               --                                          31  Tris(di-n-butylamino)-                                                                        80  -- 14.3                                                                              80.1                                                                              3.4                                                                               2.2                                             phosphine                                                                  32  Phosphorus tri(Nmethyl-                                                                       80  -- 14.2                                                                              81.3                                                                              2.1                                                                               2.4                                             anilide)                                                                   33  Diphenylphosphinic chloride                                                                   75  -- 12.3                                                                              82.2                                                                              4.1                                                                               1.4                                         34  Cyclohexylphenylphosphino-                                                                    80  -- 12.9                                                                              80.5                                                                              5.0                                                                               1.6                                             thioic chloride                                                            35  Di-n-butylphosphino-                                                                          80  -- 10.5                                                                              84.1                                                                              4.2                                                                               1.2                                             thioic acid                                                                36  Isopropyl n-hexyl                                                                             80  -- 7.7                                                                               85.3                                                                              4.8                                                                               2.2                                             phosphinic acid                                                            37  Dicyclohexylphosphino-                                                                        80  -- 13.4                                                                              78.8                                                                              4.8                                                                               3.0                                             dithioic acid                                                              38  Methyl n-octyl n-hexyl                                                                        40  15.7                                                                              78.5                                                                              5.8                                                                               -- --                                              phosphinate                                                                39  Methyl n-octyl n-hexyl                                                                        80  -- 11.4                                                                              84.5                                                                              3.1                                                                               1.0                                             phosphinate                                                                40  OMethyl diisopropyl-                                                                          80  -- 13.3                                                                              80.9                                                                              5.0                                                                               0.8                                             phosphinothioate                                                           41  Phenyl diethylphosphino-                                                                      80  -- 12.3                                                                              82.3                                                                              4.3                                                                               1.1                                             dithioate                                                                  42  Methyl dicyclohexyl                                                                           75  -- 14.5                                                                              80.3                                                                              4.5                                                                               0.7                                             phosphinate                                                                43  Hexamethylene phosphoric                                                                      80  -- 16.3                                                                              77.5                                                                              4.1                                                                               2.1                                             triamide                                                                   44  Phenyl phosphonus                                                                             75  -- 16.0                                                                              78.6                                                                              4.0                                                                               1.4                                             dichloride                                                                 45  Cyclohexylphosphonic                                                                          75  -- 13.7                                                                              81.3                                                                              3.7                                                                               1.3                                             dichloride                                                                 46  S,SDiethyl phenyl-                                                                            45  12.2                                                                              80.2                                                                              7.6                                                                               -- --                                              phosphonodithioate                                                         47  S,SDiethyl phenyl-                                                                            85  -- 8.9                                                                               88.1                                                                              3.0                                                                               --                                              phosphonodithioate                                                         48  Diethyl-n-butylphosphonate                                                                    80  -- 12.7                                                                              80.9                                                                              4.2                                                                               2.2                                         49  O,ODiethyl phenyl-                                                                            40  12.7                                                                              81.7                                                                              5.6                                                                               -- --                                              phosphonothioate                                                           50  O,ODiethyl phenyl-                                                                            80  -- 5.4                                                                               89.0                                                                              3.5                                                                               2.1                                             phosphonothioate                                                           51  O,SDiethyl phenyl-                                                                            80  -- 6.5                                                                               90.2                                                                              2.3                                                                               1.0                                             phosphonothioate                                                           52  SEthyl N,Ndiethyl                                                                             80  -- 6.4                                                                               87.6                                                                              4.5                                                                               1.5                                             Pmethyl phosphonoamide                                                         thioate                                                                    53  OEthyl phenyl phosphono-                                                                      50  10.7                                                                              82.8                                                                              6.5                                                                               -- --                                              dithioate                                                                  54  OEthyl phenyl phosphono-                                                                      90  -- 4.5                                                                               92.3                                                                              3.2                                                                               --                                              dithioate                                                                  55  OEthyl Sphenyl phenyl-                                                                        80  -- 5.5                                                                               90.1                                                                              4.4                                                                               --                                              phosphonodithioate                                                         56  2,2'-Dichlorodiethyl ether                                                                    80  -- 19.5                                                                              77.0                                                                              3.5                                                                               --                                          57  Di-n-butyl ether                                                                              85  -- 18.3                                                                              78.7                                                                              3.0                                                                               --                                          58  Di-n-octyl ether                                                                              80  -- 15.5                                                                              80.3                                                                              3.1                                                                               1.1                                         59  Di-n-octadecyl ether                                                                          40  11.1                                                                              78.8                                                                              10.1                                                                              -- --                                          60  Di-n-octadecyl ether                                                                          80  -- 6.6                                                                               87.2                                                                              4.7                                                                               1.5                                         61  Diphenyl ether 80  -- 12.8                                                                              80.5                                                                              4.7                                                                               2.0                                         62  Naphthyl ethyl ether                                                                          80  -- 8.3                                                                               85.3                                                                              3.6                                                                               2.8                                         63  Dicyclohexyl ether                                                                            80  -- 14.5                                                                              81.0                                                                              4.5                                                                               --                                          64  4-Pyridyl ethyl ether                                                                         85  -- 11.7                                                                              83.4                                                                              3.0                                                                               1.9                                         65  p-Dioxane      80  -- 10.8                                                                              82.1                                                                              5.6                                                                               1.5                                         66  Furan          80  -- 7.2                                                                               89.8                                                                              2.0                                                                               1.0                                         67  Tetrahydrofuran                                                                               80  -- 5.3                                                                               90.2                                                                              4.5                                                                               --                                          68  15-Crown-5     40  15.6                                                                              80.9                                                                              3.0                                                                               -- 0.5                                         69  15-Crown-5     80  -- 6.9                                                                               90.5                                                                              1.6                                                                               1.0                                         70  Dibenzo-18-Crown-6                                                                            40  16.2                                                                              80.0                                                                              2.6                                                                               -- 1.2                                         71  Dibenzo-18-Crown-6                                                                            80  -- 14.1                                                                              81.6                                                                              1.6                                                                               2.7                                         72  Isobutyl alcohol                                                                              80  -- 16.8                                                                              78.5                                                                              3.8                                                                               0.9                                         73  n-Octyl alcohol                                                                               80  -- 8.6                                                                               85.9                                                                              4.0                                                                               1.5                                         74  n-Tetradecyl alcohol                                                                          80  -- 10.9                                                                              83.6                                                                              3.4                                                                               2.1                                         75  n-Octadecyl alcohol                                                                           80  -- 14.5                                                                              80.8                                                                              3.5                                                                               1.2                                         76  m-Cresol       70  -- 16.8                                                                              75.8                                                                              3.2                                                                               4.2                                         77  2-(3-Tolyloxy)-3-methyl                                                                       70  -- 14.9                                                                              77.8                                                                              3.5                                                                               3.8                                             phenol                                                                     78  2,6-Di-t-Butyl-4-methyl                                                                       70  -- 10.5                                                                              82.7                                                                              3.3                                                                               3.5                                             phenol                                                                     79  2,2'-Methylenebis(4-                                                                          70  -- 9.1                                                                               83.3                                                                              3.6                                                                               4.0                                             methoxy-6-t-butyl phenol)                                                  80  4,4'-Thiobis(3-methyl-6-                                                                      75  -- 8.8                                                                               84.5                                                                              2.9                                                                               3.8                                             t-butyl phenol)                                                            81  4-Hydroxypyridine                                                                             40  10.7                                                                              82.5                                                                              5.8                                                                               -- 1.0                                         82  4-Hydroxypyridine                                                                             80  -- 7.4                                                                               85.9                                                                              3.1                                                                               3.6                                         83  Cyclohexyl alcohol                                                                            80  -- 12.6                                                                              83.1                                                                              3.1                                                                               1.2                                         84  Ethylene glycol                                                                               85  -- 12.3                                                                              83.1                                                                              3.7                                                                               0.9                                         85  Ethylene dithioglycol                                                                         85  -- 12.7                                                                              84.2                                                                              2.1                                                                               1.0                                         86  Ethylene glycol mono-n-                                                                       80  -- 16.1                                                                              79.3                                                                              3.6                                                                               1.0                                             butyl ether                                                                87  Diethylene glycol mono-                                                                       80  -- 12.7                                                                              80.9                                                                              4.9                                                                               1.5                                             n-dodecyl ether                                                            88  Propylene glycol                                                                              80  -- 13.0                                                                              83.1                                                                              2.8                                                                               1.1                                             diisopropionate                                                            89  Tripropylene glycol                                                                           80  -- 6.6                                                                               86.8                                                                              3.8                                                                               2.8                                             monostearate                                                               90  Ethylene glycol                                                                               80  -- 13.2                                                                              82.2                                                                              3.7                                                                               0.9                                             monophenyl ether                                                           91  β-Cyclodextrin                                                                           45  11.8                                                                              85.7                                                                              2.5                                                                               -- --                                          92  β-Cyclodextrin                                                                           80  -- 5.2                                                                               89.2                                                                              4.1                                                                               1.5                                         93  1,5-Sorbitan monostearate                                                                     45  14.1                                                                              80.3                                                                              5.6                                                                               -- --                                          94  1,5-Sorbitan monostearate                                                                     85  -- 12.1                                                                              83.5                                                                              3.5                                                                               0.9                                         95  Glycerin monopalmitate                                                                        85  -- 13.0                                                                              82.8                                                                              3.0                                                                               1.2                                         96  Bis(hydroxyethylthio-                                                                         40  12.0                                                                              80.7                                                                              6.3                                                                               -- 1.0                                             ethyl) ether                                                               97  Bis(hydroxyethylthio-                                                                         80  -- 10.6                                                                              85.9                                                                              2.8                                                                               0.7                                             ethyl) ether                                                               98  Bis(mercaptoethylthio-                                                                        85  -- 5.9                                                                               90.2                                                                              3.1                                                                               0.8                                             ethyl) ether                                                               99  Bis(chloroethoxyethyl)                                                                        80  -- 16.0                                                                              80.1                                                                              2.8                                                                               1.1                                             ether                                                                      100 Bis(aminoethylthioethyl)                                                                      85  -- 9.7                                                                               85.5                                                                              3.8                                                                               1.0                                             ether                                                                      101 Ethylene dithioglycol                                                                         85  -- 8.4                                                                               88.9                                                                              1.8                                                                               0.9                                             hexamer                                                                    102 Polyethylene glycol                                                                           80  -- 9.4                                                                               86.5                                                                              2.6                                                                               1.5                                             --Mn = 1,000                                                               103 Polypropylene glycol                                                                          80  -- 10.1                                                                              85.0                                                                              3.7                                                                               1.2                                             --Mn = 3,000                                                               104 Polyoxyethylene 1,5-sorbi-                                                                    40   7.4                                                                              82.5                                                                              10.1                                                                              -- --                                              tan monostearate                                                               --Mn = 1,000                                                               105 Polyoxyethylene 1,5-                                                                          80  -- 10.8                                                                              84.6                                                                              2.5                                                                               2.1                                             sorbitan monostearate                                                          --Mn = 1,000                                                               106 Polyoxyethylene glycerin                                                                      80  -- 10.7                                                                              83.5                                                                              3.0                                                                               2.8                                             monopalmitate --Mn = 800                                                   107 Polyoxyethylene dodecyl                                                                       80  -- 14.3                                                                              80.8                                                                              3.1                                                                               1.8                                             ether --Mn = 800                                                           108 Polyoxyethylene p-dodecyl-                                                                    80  -- 14.7                                                                              81.7                                                                              2.3                                                                               1.3                                             phenyl ether --Mn = 700                                                    109 Polyoxyethylene lauryl-                                                                       80  -- 11.9                                                                              84.4                                                                              2.7                                                                               1.0                                             amine --Mn = 600                                                           110 Polyoxyethylene lauryl-                                                                       80  -- 15.8                                                                              80.3                                                                              3.0                                                                               0.9                                             amide --Mn = 600                                                           __________________________________________________________________________      ##STR18##                                                                                                                                                     ##STR19##                                                                                                                                                     ##STR20##                                                                                                                                                     ##STR21##                                                                                                                                                     ##STR22##                                                                 

We claim:
 1. A process for producing in high yield and high selectivity a chlorinated phenoxytoluene derivative represented by the formula ##STR23## wherein R¹ and R₂ are the same or different and are each hydrogen, halogen, cyano, nitro, alkyl, alkoxyl, alkoxycarbonyl, halogenoalkyl, acyl, acyloxy, aryl, aralkyl or aralkyloxy, R³ is hydrogen or chlorine, which comprises chlorinating at a temperature of 0° to 150° C. a phenoxytoluene derivative represented by the formula ##STR24## wherein R¹ and R² are same as above, with chlorine in an amount that provides said chlorinated phenoxytoluene derivative, in the presence of about 0.001 to 50 wt. % based on said phenoxytoluene derivative of at least one compound selected from the group consisting of nitrogen-containing compound, sulfur-containing compound, phosphorus-containing compound and oxygen-containing compound which is capable of forming a charge-transfer complex with chlorine, chlorine radical or organic halogen compound, together with about 0.001 to 20 wt. % based on said phenoxytoluene derivative of radical initiator and about 1 to 20 times the weight of said phenoxytoluene derivative of an organic halogen compound.
 2. A process as defined in claim 1 wherein the nitrogen-containing compounds are those represented by the formulae ##STR25## in which R⁴ to R⁶ are each hydrogen, alkyl having 1 to 20 carbon atoms, hydroxyalkyl having 1 to 10 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 10 carbon atoms with or without a substituent, two or three of R⁴ to R⁶ may form a ring, R⁷ is alkylene having 2 to 8 carbon atoms or arylene having 6 to 10 carbon atoms.
 3. A process as defined in claim 1 wherein the sulfur-containing compounds are those represented by the formulae ##STR26## R⁸ and R⁹ are each alkyl having 1 to 20 carbon atoms; cycloalkyl having 5 to 8 carbon atoms; aryl having 6 to 10 carbon atoms; heterocyclic group having nitrogen, sulfur, oxygen atom, etc, and R⁸ and R⁹ may conjointly form an alicyclic or heterocyclic ring, a is an integer of 1 to 8, A and B is R¹¹, NR¹² R¹³, NR¹² NR¹² R¹³, NR¹² NCR¹² R¹³, SR¹², SNR¹² R¹³, SHNR¹² R¹³ R¹⁴ or OR¹⁴, R¹⁰ to R¹⁴ are hydrogen, alkyl having 1 to 20 carbon atoms aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic ring and R¹² and R¹³ or R¹² to R¹⁴ may conjointly form a heterocyclic ring, R¹² and R¹³ further include acyl having 1 to 20 carbon atoms with or without a substituent and R¹¹ does not include hydrogen, A and B may conjointly form an alicyclic or heterocyclic ring, D is NR¹², sulfur atom or oxygen atom, E is R¹⁵, R¹⁵ SR¹⁵, R¹⁵ SO₂ R¹⁵, C(S)NHR¹⁵ NHC(S), R¹⁵ NHC(S)NHR¹⁵, R¹⁵ NR¹² R¹⁵, R¹⁵ C(O)R.sup. 15 or R¹⁵ C(S)R¹⁵, b is 0 or an integer of 1 to 4 but b is 1 when D is NR¹² or oxygen atom, c is 0 or 1, F is R¹⁶, CN, NR¹⁷ R¹⁸, C(O)R¹⁷, S(O)R¹⁷, C(O)OR¹⁷, C(O)NR¹⁷ R¹⁸, C(O)SR¹⁷, R¹⁹ C(O)OR¹⁷, R¹⁹ C(O)NR¹⁷ R¹⁸, R¹⁹ SR¹⁷ R¹⁹ NR¹⁷ R¹⁸, R¹⁹ C(O)R¹⁷ or HNR¹⁷ R¹⁷ R¹⁸, R¹⁶ to R¹⁸ are hydrogen; alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic froup with or without a substituent; but R¹⁶ is alkyl, aryl or alicyclic group having a substituent when f is 0, R¹⁹ is alkylene having 1 to 12 carbon atoms or arylene having 6 to 10 carbon atoms with or without a substituent, G is R¹⁹, R¹⁹ C(O)R¹⁹, C(O)R¹⁹ C(O) or C(O), L is sulfur atom or NR¹⁷, d is 1 to 8, e is 1 to 50 and f is 0 or 1 to 50, and F further includes R¹⁹ OR¹⁷ and R¹⁹ OR¹⁹ OR¹⁹ when d is other than
 1. 4. A process as defined in claim 1 wherein the phosphorus-containing compounds are those represented by the formulae ##STR27## in which M, Q and T are hydrogen, halogen, R²⁰, WR²⁰ or NR²⁰ R²¹, R²⁰ and R²¹ are the same or different and are hydrogen, alkyl having 1 to 20 carbon atoms; aryl having 6 to 10 carbon atoms; amino; alicyclic or heterocyclic ring, W is oxygen atom or sulfur atom, and M and Q, or Q and T may conjointly form an alicyclic or heterocyclic ring, and at least two of M, Q and T are organic group other than hydrogen.
 5. A process as defined in claim 1 wherein the oxygen-containing compounds are those represented by the formulae ##STR28## in which R²² and R²³ are each alkyl having 1 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, alicyclic or heterocyclic ring, and R²² and R²³ may form an alicyclic, heterocyclic or large polyether ring, R²⁴ and R²⁵ are the same or different and are alkylene having 2 to 8 carbon atoms, X is oxygen atom, sulfur atom, alkoxyl, alkylamino or alkylamido, each having 1 to 20 carbon atoms and with or without a substituent, aryloxy having 6 to 10 carbon atoms, oxyalicyclic or oxyheterocyclic ring, each having or not having a substituent, Y is hydrogen, halogen, hydroxyl, mercapto, alkyl having 1 to 20 carbon atoms, carboxylalkyl having 2 to 20 carbon atoms or alkylamino having 1 to 20 carbon atoms, Z is oxygen atom or sulfur atom, g is 1 to 50, h is 0 to 25 and i is 1 to 6 but i is 2 when X is oxygen atom or sulfur atom.
 6. A process as defined in claim 1 wherein the amount is about 0.01 to 30 wt % based on the starting phenoxytoluene derivative.
 7. A process as defined in claim 1 wherein the organic halogen compounds are those represented by the formulae ##STR29## in which Hal means halogen atom, m is 0 or an integer of 1 to 3, m' is 0 or an integer of 1 to 2, m" is 0 or 1, n is an integer of 1 to 6, or chlorinated paraffin.
 8. A process as defined in claim 7 wherein the organic halogen compound is carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, chloroform, bromoform, iodoform, methylene chloride, methylene bromide, dichloroethane, trichloroethane, tetrachloroethane, tetrachloroethylene or hexachlorocyclohexane.
 9. A process as defined in claim 1 wherein the amount of 5 to 10 times the weight of the starting phenoxytoluene derivative.
 10. A process as defined in claim 1 wherein the radical initiator is an azo compound or peroxide.
 11. A process as defined in claim 10 wherein the radical initiator is azobisisobutyronitrile or benzoyl peroxide.
 12. A process as defined in claim 1 wherein the amount is about 0.01 to 15 wt % of the starting phenoxytoluene derivative.
 13. A process as defined in claim 1 wherein chlorine is blown into the reaction system in an amount of about 0.5 to 10 mole % per minute of the starting phenoxytoluene derivative.
 14. A process as defined in claim 13 wherein the amount is about 2 to 5 mole % per minute of the starting phenoxytoluene derivative. 